Adamantane derivatives, compositions of matter containing same, processes for preparing said adamantane derivatives and said compositions, and organoleptic and deodorancy uses of said adamantane derivatives and said compositions

ABSTRACT

Described are hydroxy adamantane compounds and derivatives thereof and a process for preparing same.

SUMMARY OF ADAMANTANE DERIVATIVES AND PROPERTIES

The following Table A summarizes the nature of the compounds of ourinvention and their aroma properties:

                  TABLE A                                                         ______________________________________                                        Composition of Matter                                                                        Perfumery Properties                                           ______________________________________                                        The compound having                                                                          A sandalwood, woody,                                           the structure: patchouli, rhubarb, ginger,                                     ##STR1##      minty and amyris aroma with amyris, camphoraceous,                            patchouli, woody, and piney topnotes.                          produced according to                                                         Example III, bulked                                                           fractions 6-9.                                                                The compound having                                                                          A camphoraceous, ginger                                        the structure: cardamon and woody aroma                                        ##STR2##      profile.                                                       produced according to                                                         Example IIIA.                                                                 The compound having                                                                          A cedarwood-like, sandalwood-                                  the structure: like, camphoraceous, woody,                                     ##STR3##      minty and earthy aroma with cedarwood, sandalwood,                            patchouli, camphoraceous, herbaceous, incense and olibanum                    topnotes.                                                      prepared according to                                                         Example IV, bulked                                                            fractions 8-18.                                                               The compound having                                                                          A cedarwood-like, patchouli,                                   the structure: vetiver, peppery, grapefruit                                    ##STR4##      peel-like and camphoraceous aroma with vetiver and                            grapefruit peel-like topnotes.                                 prepared according                                                            to Example V(B),                                                              bulked fractions 7-9                                                          The compound having                                                                          A woody, rose-like and                                         the structure: peony-like aroma with floral,                                   ##STR5##      sweet pea, rose and peony topnotes.                            prepared according to                                                         Example VI, bulked                                                            fractions 10-16.                                                              The compound having                                                                          An ambery, woody and                                           the structure: cedarwood-like aroma with                                       ##STR6##      fruity and woody topnotes.                                     prepared according to                                                         Example VI, bulked                                                            fractions 5-19.                                                               The compound having                                                                          A camphoraceous aroma with                                     the structure: early morning forest path,                                      ##STR7##      green, piney, woody and camphoraceous topnotes.                prepared according to                                                         Example VII.                                                                  The compound having                                                                          A spicy, ginger root,                                          the structure: rosemary and camphoraceous                                      ##STR8##      aroma with green, woody and ginger root topnotes.              prepared according to                                                         Example X, bulked                                                             fractions 4 and 5.                                                            The compound having                                                                          A woody, ambery, vetiver,                                      the structure: cedarwood, piney and                                            ##STR9##      chrysanthemum-like aroma with woody, amber and olibanum                       topnotes.                                                      prepared according to                                                         Example XI, bulked                                                            fractions 5-9.                                                                The compound having                                                                          A woody, amber, vetiver,                                       the structure: cedarwood, piney and                                            ##STR10##     chrysanthemum-like aroma with woody, amber and olibanum                       topnotes.                                                      prepared according to                                                         Example XIII, bulked                                                          fractions 2-18.                                                               The mixture of compounds                                                                     A green, woody and fir                                         having the structures:                                                                       balsam-like aroma profile.                                      ##STR11##                                                                     ##STR12##                                                                     ##STR13##                                                                    and                                                                            ##STR14##                                                                    prepared according to                                                         Example XIV, fraction 6.                                                      The mixture of compounds                                                                     A camphoraceous aroma with sweet                               having the structures:                                                                       camphoraceous topnotes.                                         ##STR15##                                                                     ##STR16##                                                                     ##STR17##                                                                     ##STR18##                                                                     ##STR19##                                                                    and                                                                            ##STR20##                                                                    prepared according to                                                         Example XV.                                                                   The compound having                                                           the structure:                                                                 ##STR21##                                                                    bulked fractions 4-6                                                          produced according                                                            to Example XII.                                                               ______________________________________                                    

BACKGROUND OF THE INVENTION

This invention relates to adamantane derivatives which have thestructure: ##STR22## substituted at least at the "2", "4" and "8"positions, thusly: (a) at the "2" position with an oxygen atom;

(b) at the "4" position with a carbon atom; and

(c) at the "8" position with a methyl group

and uses thereof in augmenting or enhancing the aroma or taste ofconsumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) fragrances to (or in)various consumable materials. These substances are used to diminish theuse of natural materials some of which may be in short supply and toprovide more uniform properties in the finished product.

Long-lasting, substantive and intense sandelwood, woody, patchouli,rhubarb, ginger, minty, amyris, camphoraceous, cardamon, earthy,cedarwood-like, vetiver, peppery, grapefruit peel-like, rose-like,ambery, spicy, ginger root, rosemary, piney, chrysanthemon-like, greenand fir balsam-like aromas with sweet, amyris, camphoraceous, patchouli,woody, piney, cedarwood, sandalwood, herbaceous, incense, olibanum,vetiver, grapefruit peel-like, floral, sweet pea, rose, peony, fruity,early morning forest path, green, ginger root and amber topnotes aredesirable in several types of perfume compositions, perfurmed articles,colognes, deodorizing compositions and odor maskant materials.

The use of tricyclic alcohol derivatives in perfumery for augmenting orenhancing the aromas of perfume compositions, perfumed articles andcolognes is well known the art. Thus, Inamoto, et al in U.S. Pat. No.4,036,893 discloses the use in perfumery of the compound having thestructure: ##STR23## Inamoto, et al in U.S. Pat. No. 4,169,958 alsodiscloses the use of the tricyclic alcohol having the structure:##STR24## in perfumery. Light, et al in U.S. Pat. No. 3,996,169discloses the use of the compound having the structure: ##STR25## inperfumery. Inamoto, et al in U.S. Pat. No. 4,169,958 also discloses theuse of the tricyclic alcohol having the structure: ##STR26## inperfumery. Light, et al in U.S. Pat. No. 3,996,169 discloses the use ofthe compound having the structure: ##STR27## in perfumery. Inamoto, etal in U.S. Pat. No. 4,036,892 discloses the use of the compound havingthe structure: ##STR28## and in U.S. Pat. No. 4,036,892 discloses theuse in perfumery of the compound having the structure: ##STR29## The usein perfumery of the compound having the structure: ##STR30## isdisclosed in Chemical Abstracts, Volume 109, 9, 1988, No. 6759v(abstract of Koltsa, et al Zh.Obshch.Khim., 1987, 57 (11) 2620-9.

Light, et al at U.S. Pat. No. 4,439,354 discloses the genus of compoundsdefined according to the structure: ##STR31## for use in perfumerywherein R₁ represents hydrogen, methyl or acetyl and R₂, R₃, R₄ and R₅each represent hydrogen, methyl or ethyl.

Light, et al in U.S. Pat. No. 3,996,169 discloses the genus of compoundsdefined according to the structure: ##STR32## where one or more of the Rgroups represents hydrogen or methyl.

Adamantane derivatives and adamantane itself are known for use inaugmenting or enhancing the aroma of perfume compositions, perfurmedarticles and colognes. Thus, the perfume use of compounds havig thestructures: ##STR33## is disclosed in Chemical Abstracts, Volume 71, No.94695w (abstract of Netherlands Published Application No. 6715903, May28, 1969). Japan Kokai No. 75/25742 Published on Mar. 18, 1975 andabstracted at Chem. Abstracts, Volume 84, No. 35214j and Japan KokaiTokkyo Koho 78: 145920 Published on Dec. 19, 1978 and abstracted atChem. Abstracts, Volume 90, No. 142085p discloses the perfume use ofadamantane itself having the structure: ##STR34##

Synthesis of various oxygen-substituted adamantane derivative is wellknown in the prior art.

Mlinaric-Magerski and Magerski, J. Am. Chem. Soc., 1983, 105, pages7389-7395 discloses the compound having the structure: ##STR35## at page7390 and discloses the reaction squence: ##STR36## at page 7389.

Haliden-Aberton, J. Org. Chem., Volume 46, No. 3, 1981, pages 538-546discloses the reaction sequence: ##STR37## at pages 539 and 544.

Drivas and Mison, Tetrahedron Letters, Volume 22, 1981, at pages 641-644discloses at page 643 the reaction sequence: ##STR38##

Kovalev, et al. Chem. Abstracts, Volume 109, 1988, No. 22553d (abstractof Zh. Org. Khim., 1987, 23 (9), 1882-6 discloses the compounds havingthe structures: ##STR39## and discloses the reaction sequence: ##STR40##

However, the adamantane derivatives of our invention have unexpected,unobvious and advantageous properties with respect to the compounds ofthe prior art. Nothing in the prior art explicitly or implicitly setsforth the adamantane derivatives of our invention or their uses.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. A is the GLC profile for the reaction product of Example Acontaining the compound having the structure: ##STR41##

FIG. 1 is the GLC profile for the reaction product of Example Icontaining the compound having the structure: ##STR42## (Conditions:K-20M column programmed at 100°-220° C. at 8° C. per minute).

FIG. 2 is another GC scan for the reaction product of Example Icontaining the compound having the structure: ##STR43##

FIG. 3 is the NMR spectrum for the compound having the structure:##STR44## prepared according to Example I.

FIG. 4 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR45##

FIG. 5 is the GLC profile for the reaction product of Example IIIcontaining the compound having the structure: ##STR46## (Conditions:Carbowax column programmed at 130°-220° C.).

FIG. 5A is the GLC profile for the crude reacton product of ExampleIII(A) containing the compound having the structure: ##STR47## and, (inaddition, the compounds having the structures: ##STR48## wherein each ofthe representations of the foregoing structures (i) and (ii) showsmixtures and wherein in the mixtures in each of the compounds one of thedashed lines is a carbon-carbon double bond and the other of the dashedlines is a carbon-carbon single bond.

FIG. 5B is the NMR spectrum for the compound having the structure:##STR49##

FIG. 5C is the NMR spectrum for the mixture of compounds having thestructures: ##STR50## wherein in the mixture one of the dashed lines isa carbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond.

FIG. 6 is the GLC profile for the crude reaction product of Example IVcontaining the compound having the structure: ##STR51## (Conditions:Carbowax column programmed at 130°-220° C.).

FIG. 7 is the NMR spectrum for the compound having the structure:##STR52## prepared according to Example IV.

FIG. 8 is the GLC profile for the crude reaction product of Example V(A)containing the compound having the structure: ##STR53## (Conditions:Carbowax column programmed at 130°-220° C.).

FIG. 9 is the NMR spectrum for the isomer having the structure:##STR54## prepared according to Example V(A).

FIG. 10 is the NMR spectrum for the isomer having the structure:##STR55## prepared according to Example V(A).

FIG. 11 is the GLC profile for the crude reaction product of ExampleV(B) containing the compound having the structure: ##STR56##(Conditions: Carbowax column programmed at 130°-220° C.).

FIG. 12 is the GLC profile for the crude reaction product of Example VIcontaining the compound having the structure: ##STR57## (Conditions:Carbowax column programmed at 130°-220° C.).

FIG. 13 is the NMR spectrum for the compound having the structure:##STR58## prepared according to Example VI.

FIG. 14 is the GLC profile for the crude reaction product of Example VIIcontaining the compound having the structure: ##STR59## (Conditions:Carbowax column programmed at 130°-220° C.).

FIG. 15 is the NMR spectrum for the compound having the structure:##STR60## prepared according to Example VII.

FIG. 16 is the GLC profile for the crude reaction product of ExampleVIII containing the compound having the structure: ##STR61##

FIG. 17 is the NMR spectrum for the peak indicated by reference numeral161 in FIG. 16, the compound having the structure: ##STR62##

FIG. 18 is the NMR spectrum for the peak indicated by reference numeral162 in FIG. 16; the compound having the structure: ##STR63##

FIG. 19 is the NMR spectrum for the peak indicated by reference numeral163 in FIG. 16 for a compound produced according to Example VIII.

FIG. 20 is the NMR spectrum for the peak indicated by reference numeral164 in FIG. 16; the compound having the structure: ##STR64##

FIG. 21 is the GLC profile for the crude reaction product of Example IXcontaining the compound having the structure: ##STR65##

FIG. 22 is the GLC profile for the crude reaction product of Example Xcontaining the compound having the structure: ##STR66## (Conditions:Carbow column programmed at 130°-220° C.).

FIG. 23 is the NMR spectrum for the compound having the structure:##STR67## produced according to Example X.

FIG. 24 is the GLC profile for the crude reaction product producedaccording to Example XI containing the compound having the structure:##STR68## (Conditions: Carbowax column programmed at 130°-220° C.).

FIG. 25 is the NMR spectrum for the compound having the structure:##STR69## produced according to Example XI.

FIG. 26 is a partial side elevation and partial sectional view of anapparatus for forming polymer pellets containing at least one of theadamantane derivatives of our invention.

FIG. 27 is a section taken along line 27--27 of FIG. 26.

FIG. 28 is the GLC profile for the crude reaction product of Example XIIcontaining the compound having the structure: ##STR70## (Conditions:SE-30 column programmed at 130°-220° C. at 8° C. per minute).

FIG. 29 is the GLC profile for the crude reaction product of ExampleXIII containing the compound having the structure: ##STR71##(Conditions: SE-30 column programmed at 130°-220° C. at 8° C. perminute).

FIG. 30 is the GLC profile for the crude reaction product of Example XIVcontaining the compounds having the structures: ##STR72## (Conditions:SE-30 column programmed at 130°-220° C. at 8° C. per minute).

FIG. 31 is the GLC profile for distillation fracton 6 of thedistillation product of the reaction product of Example XIV.

FIG. 32 is the GLC profile for distillation fraction 7 of thedistillation product of the reaction product of Example XIV (Conditions:SE-30 column programmed at 130°-220° C. at 8° C. per minute).

FIG. 33 is the NMR spectrum for the peak indicated by reference numeral303 of the GLC profile of FIG. 30; the compound having the structure:##STR73##

FIG. 34 is the NMR spectrum for the peak indicated by reference numeral304 of the GLC profile of FIG. 30; the compound having the structure:##STR74##

FIG. 35 is the NMR spectrum for the peak indicated by reference numeral305 on the GLC profile of FIG. 30; for the compound having thestructure: ##STR75##

FIG. 36 is the NMR spectrum for distillation fraction 6 of thedistillation product of the reaction product of Example XIV containingthe compounds having the structures: ##STR76##

FIG. 37 is the NMR spectrum for distillation fraction 8 of thedistillation product of the reaction product of Example XIV containingthe compounds having the structures: ##STR77##

FIG. 37A is the GLC profile for the crude reaction product of Example XVcontaining the compounds having the structures: ##STR78##

FIG. 37B is the GLC profile for distillation fraction 3 of thedistillation product of the reaction product of Example XV containingthe compounds having the structures: ##STR79##

FIG. 37C is another GLC profile of distillation fraction 3 of thedistillation product of the reaction product of Example XV.

FIG. 38 is the NMR spectrum for peak group 371 of the GLC profile ofFIG. 37B of distillation fraction 3 of the distillation product of thereaction product of Example XV for the compound having the structure:##STR80##

FIG. 39 is the GLC profile for distillation fraction 6 of thedistillation product of the reaction product of Example XV containingthe compounds having the structures: ##STR81##

FIG. 40 is the NMR spectrum for peak group 392 of the GLC profile ofFIG. 39 for distillation fraction 6 of the distillation product of thereaction product of Example XV; one or a mixture of the compounds havingthe structures: ##STR82##

FIG. 41 is the NMR spectrum for the peak group 393 of the GLC profile ofFIG. 39 of the distillation fraction 6 of the distillation product ofExample XV and is for the compound having the structure: ##STR83##

FIG. 42 is the NMR spectrum of peak group 394 of the GLC profile of FIG.39 for distillation fraction 6 of the distillation product of thereaction product of Example XV; and is for the compound having thestructure: ##STR84## the starting material for the reaction.

FIG. 43 is the NMR spectrum for the peak indicated by reference numeral395 of the GLC profile of FIG. 39 for distillation fraction 6 of thedistillation product of the reaction product of Example XV; and is forone or both of the compounds having the structures: ##STR85##

FIG. 44 is the NMR spectrum for the peak indicated by reference numeral372 of the GLC profile of FIG. 37C; and is for one or both of theepimers having the structures: ##STR86##

FIG. 45 is the GLC profile for the crude reaction product of Example XVIcontaining the compound having the structure: ##STR87##

FIG. 46 is the NMR spectrum for the compound having the structure:##STR88## produced according to Example XVI.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. A is the GLC profile for the crude reaction product of Example Acontaining the compound having the structure: ##STR89## The peakindicated by reference numeral 5 is the peak for the compound having thestructure: ##STR90##

FIG. 1 is the GLC profile for the crude reaction product of Example Icontaining the compound having the structure: ##STR91## (Conditions:K-20 M column programmed at 100°-220° C. at 8° C. per minute). The peakindicated by reference numeral 10 is the peak for the compound havingthe structure: ##STR92##

FIG. 2 is another GLC profile for the reaction product of Example I(Conditions: Carbowax column programmed at 130°-220° C.). The peakindicated by reference numeral 21 is the peak for the compound havingthe structure: ##STR93## The peaks indicated by reference numerals 22and 23 are for the compounds having the structures: ##STR94## whereinthese structures are representative of mixtures and in the mixture ineach of the compounds one of the dashed lines is a carbon-carbon doublebond and the other of the dashed lines is a carbon-carbon single bond.

FIG. 4 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of Example II (Conditions: K-20 M column programmedat 100°-220° C. at 8° C. per minute). The peak indicated by referencenumeral 41 is the peak for the compound having the structure: ##STR95##

FIG. 5 is the GLC profile for the crude reaction product of Example III.The peak indicated by reference numeral 51 is the peak for the compoundhaving the structure: ##STR96## The peak indicated by reference numerals52 and 53 are for the solvent used in the reaction mass. (Conditions:Carbowax column programmed at 130°-220° C. at 8° C. per minute).

FIG. 5A is the GLC profile for the crude reaction product of ExampleIIIA. The peak indicated by reference numeral 55 is the peak for thecompound having the structure: ##STR97## The peak indicated by referencenumeral 54 is the peak for the mixture of compounds defined according tothe structure: ##STR98## representative of a mixture of compoundswherein in the mixture in each of the compounds one of the dashed linesis a carbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond. The peak indicated by reference numeral 56and 57 is for a mixture of compounds defined according to the structure:##STR99## wherein in the mixture one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond. (Conditions: Carbowax column programmed at130°-220° C. at 8° C. per minute).

FIG. 8 is the GLC profile for the crude reaction product of Example V(A)(Conditions: Carbowax column programmed at 130°-220° C. at 8° C. perminute). The peak indicated by reference numeral 81 is the peak for thecompound having the structure: ##STR100## The peak indicated byreference numeral 82 is the peak for the compound having the structure:##STR101##

FIG. 16 is the GLC profile for the crude reaction product of ExampleVIII (Conditions: Carbowax column programmed at 130°-220° C. at 8° C.per minute). The peak indicated by reference numeral 161 is for one ofthe isomers having the structure: ##STR102## The peak indicated byreference numeral 162 is for another isomer having the structure:##STR103## The peak indicated by reference numeral 163 is the peak foranother isomer of the compound having the structure: ##STR104## The peakindicated by reference numeral 164 is for isomers of the compound havingthe structure: ##STR105##

FIG. 22 is the GLC profile for the crude reaction product of Example X.The peak indicated by reference numeral 2200 is the peak for thecompound having the structure: ##STR106## (Conditions: Carbowax columnprogrammed at 130°-220° C. at 8° C. per minute).

Referring to FIGS. 26 and 27 in particular, the apparatus used inproducing polymeric fragrances containing one or more of the adamantanederivatives comprises a device for forming scented polyolefin (forexample) pellets, which comprises a vat or container 212 into which amixture of polyolefins such as polyethylene and an aromatic substance orscented material is placed (in this case at least one of the adamantanederivatives of our invention). The container is closed by an airtightlid 228 and clampled to the container by bolts 265. A stirrer 273traverses the lid or cover 228 in airtight manner and is rotated in asuitable manner. A surrounding cyliner 212 having heating coils 212Awhich are supplied with electric current through cable 224 from arheostat or control 216 is operated to maintain a temperature inside thecontainer 212 such that polyethylene or other thermoplastic polymer inthe container will be maintained in the molten or liquid state. It hasbeen found advantageous to employ a colorless odorless polymer (e.g.,polyethylene) with viscosity ranging between 180 and 220 saybolt secondsand having a melting point in the range of 200°-280° F. The heater 212Ais operated to maintain the upper portion of the container 212 within atemperature range of from 250°-350° F. The bottom portion of thecontainer is heated by means of heating coils 212A heated through acontrol 220 connected thereto through a connecting wire 222 to maintainthe lower portion of the container within a temperature range of from250°-350° F.

Thus, polymer (e.g., polyethylene) is added to container 212 and isheated from 10-12 hours whereafter a scemted aroma imparting material(at least one of the adamantane derivatives of our invention) is addedquickly to the melt. The material must be compatible with the polyolefinand forms a homogeneous liquid melt therewith. The scented material isof a type for the particular aroma desired and formulated specificallyfor the scenting purpose for which the polyolefin will be employed.

Generally about 5-30% by weight of the scented material (containing atleast one of the adamantane derivatives of our invention) are added tothe polyolefin.

After the scent imparting material (e.g., a composition containing oneof the adamantane derivatives of our invention) is added to thecontainer 212, the mixture is stirred for a few minutes, for example,5-15 minutes and maintained within the temperature range as indicatedpreviously by heating coils 212A. The controls 216 and 220 areconnected, respectively, through cables 214 and 222, respectively, toheating coils 212A. The said cotnrols 216 and 220 are also connectedthrough cables 224 and 226, respectively, to a suitable power supply ofelectric current for supplying the electric power to the heating coils212A for heating purposes.

Thereafter the valve "V" is opened permitting the mass to flow outwardlythrough conduit 218/232 having a multiplicity of orifices 234 adjacentto the lower side thereof. The outer end of the conduit 218/232 isclosed so that the liquid polymer (e.g., polyolefin) and aroma impartingmaterial (e.g., at least one of the adamantane derivatives of ourinvention) will continuously drop through orifices 234 downwardly fromconduit 232. During this time the temperature of the polymer (e.g.,polyethylene or polyolefin) and scent imparting material (e.g., at leastone of the adamantane derivatives of our invention) is accuratelycontrolled so that a temperature in the range of from about 2100°-275°F. will exist in the conduit 218/232. The regulation of the temperaturethrough the controls 216 and 220 is essential in order to insuretemperature balance to provide for the continuous dropping or drippingof molten polymer (e.g., polyethylene) and scenting material (e.g., oneor more of the adamantane derivatives of our invention) mixture throughthe orifices 234 at a rate which will insure the formation of droplets236 which will fall downwardly onto a moving conveyor belt 238 caused torun between conveyor wheels 240 and 242 beneath the conduit 232.

When the droplets 236 fall onto the conveyor 238 they form pellets 244which harden almost instantaneously and fall off the end of the conveyor238 into a container 245 and utilized in processes as illustrated,infra.

A feature of this aspect of the process of our invention is theprovision for moistening of the conveyor belt 238 to insure rapidformation of the solid polymeric (e.g., polyolefin) scented pellets 244without sticking to material which will not normally stick to a meltedplastic. A moistening means 248 insures a sufficiently cold temperatureof the belt surface for adequate formation of the pellets 244. Theadequate moistening means comprises a container 250 which iscontinuously fed with water 254 to maintain a level for moistening asponge element 256 which bears against the exterior of the belt 238.

FIG. 30 is the GLC profile for the crude reaction product of Example XIV((Conditions: SE-30 column programmed at 130°-220° C. at 8° C. perminute).

The peak indicated by reference numeral 303 is the peak for the mixtureof compounds defined according to the structure: ##STR107## The peakindicated by reference numeral 304 is the peak for the compound havingthe structure: ##STR108##

The peak indicated by reference numeral 305 is the peak for the mixtureof compound having the structure: ##STR109##

The peak indicated by reference numeral 301 is the peak for the methanolsolvent. The peak indicated by reference numeral 302 is the peak for thetoluene solvent. (Conditions: SE-30 column programmed at 130°-220° C.).

FIG. 37A is the GLC profile for the crude reaction product of Example XV(Conditions: Carbowax column programmed at 130°-220° C. at 8° perminute). The peak group indicated by reference numeral 370 is for thecompound having the structure: ##STR110##

FIG. 37B is the GLC profile for distillation fraction 3 of thedistillation product of the reaction product of Example XV. The peakgroup indicated by reference numeral 371 is for the compound having thestructure: ##STR111## (Conditions: Carbowax column programmed at130°-220° C. at 8° C. per minute).

FIG. 37C is the GLC profile for distillation fraction 3 of thedistillation product of the reaction product of Example XV. The peakindicated by reference numeral 372 is the peak for the isomer or mixtureof isomers of epimers having the structures: ##STR112##

FIG. 39 is the GLC profile for distillation fraction 6 of thedistillation product of the reaction product of Example XV. The peakindicated by reference numeral 395 is the peak for one or both of theepimers having the structures: ##STR113## The peak indicated byreference numeral 394 is the peak for a starting material having thestructure: ##STR114## The peak indicated by reference numeral 393 is thepeak for the compound having the structure: ##STR115## The peakindicated by reference numeral 392 is the peak for one or both of thecompounds having the structures: ##STR116## The peak indicated byreference numeral 391 is the peak for the compound having the structure:##STR117##

FIG. 45 is the GLC profile for the crude reaction product of Example XVI(Conditions: Carbowax column programmed at 130°-220° C. at 8° C. perminute). The peak indicated by reference numeral 450 is the peak for thecompound having the structure: ##STR118## The peak indicated byreference numeral 451 is the peak for the compounds defined according tothe structure: ##STR119##

SUMMARY OF THE INVENTION

Our invention concerns adamantane derivatives defined according to thebasic structure: ##STR120## substituted at least at the "2", "4" and "8"positions, thusly: (a) at the "2" position with a oxygen atom;

(b) at the "4" position with a carbon atom; and

(c) at the "8" position with a methyl group.

More specifically, our invention concerns adamantane derivatives definedaccording to the generic structure: ##STR121## wherein X is a moietyselected from the group consisting of the structures: ##STR122## whereinY is a moiety selected from the group consisting of the structures:##STR123## wherein W is no moiety or is selected from the groupconsisting of hydrogen, hydroxy and lower alkoxy; wherein the dashedline represented by:

is a carbon-carbon single bond or a carbon carbon double bond; whereinthe dashed line represented by:

is no bond or is an ether moiety having the structure: ##STR124##wherein the line represented, thusly:

is a carbon-carbon single bond, a carbon-carbon double bond or acarbon-hydrogen single bond; wherein R₁ is selected from the groupconsisting of hydrogn, lower alkyl and lower acyl; and wherein R₂ isselected from the group consisting of hydrogen and lower alkyl; with theprovisos that:

(1) when the dashed line:

is a carbon-carbon double bond then Y is hydrogen, the line

is a single bond; W is no moiety and X is selected from the groupconsisting of: ##STR125## (2) when the dashed line:

is a carbon-carbon single bond and the line:

is a carbon-carbon single bond then either:

(1) Y is selected from the group consisting of: ##STR126## and X isselected from the group consisting of: ##STR127## or (2) the moiety:##STR128## represents a moiety selected from the group consisting of anenol ether moiety having the structure: ##STR129## and a lactone moietyhaving the structure: ##STR130## (3) when the line:

is a carbon-carbon double bond and the dashed line:

is a carbon-carbon single bond then the moiety: ##STR131## is an ethermoiety having the structure: ##STR132## and (4) when the dashed line:

is a carbon-carbon single bond and the line:

is a carbon-hydrogen bond and Y is: ##STR133## then W is selected fromthe group consisting of hydrogen, hydroxy and lower alkoxy;

and uses thereof in augmenting or enhancing the aroma or taste ofconsumable materials including perfume compositions, perfumed articles(e.g., solid or liquid anionic, cationic, nonionic or zwitterionicdetergents, fabric softeners, fabric softener articles, cosmeticpowders, hair preparations and perfumed polymers), colognes, smokingtobacco compositions, smoking tobacco articles, deodorizing articles andcompositions and malodor maskants.

Our invention also relates to processes for preparing such adamantanederivatives using the terpene having the structure: ##STR134## as astarting material and producing by means of "oxo" reaction the aldehydehaving the structure: ##STR135## and producing therefrom theintermediate having the structure: ##STR136## by means of reaction ofthe compound having the structure: ##STR137## with formaldehyde via a"formylation" reaction as more specifically set forth in United KingdomPatent 2,054,557 published on Feb. 18, 1981 the specification of whichis incorporated by reference herein.

The compound having the structure: ##STR138## is further reacted bymeans of heating in the absence of acid and in the presence of a basicmaterial such as sodium bicarbonate or an amine according to thereaction mechanism: ##STR139## or according to the actual reaction:##STR140##

The reactions to prepare the compound having the structure: ##STR141##The resulting compounds defined according to the structure: ##STR142##may then be further reacted to form a ketone by means of oxidationhaving the structure: ##STR143## according to the reaction: ##STR144##The resulting ketone may be used "as is" for its fragrance, deodorancyor tobacco flavorant properties or it may be reacted with hydrogenwhereby the methylene group is reduced to a methyl group to form thesaturated ketone having the structure: ##STR145## according to thereaction: ##STR146##

Either ketone may be used "as is" or may be further reacted with aGrignard reagent or an alkyl lithium compound to produce tertiaryalcohols according to the reaction: ##STR147## followed by thehydrolysis reaction: ##STR148## wherein the dashed line is acarbon-carbon double bond or a carbon-carbon single line; wherein Mrepresents Li, MgBr, MgCl or MgI and where R₂ represents lower alkyl.

The resulting tertiary alcohol may be then further reacted with anacylating compound or with any etherifying compound according to thereaction: ##STR149## wherein R₁ is an acyl moiety or an alkyl moiety andZ represents a halogen or sulfate moiety.

In the alternative, the compound having the structure: ##STR150## may bereacted via an "oxo" reaction with carbon monoxide and hydrogen atstandard oxo reaction conditions to form a mixture of compoundsaccording to the reaction: ##STR151## The resulting mixture may beseparated by means of fractional distillation to form individualcompounds, e.g., compounds having the structures: ##STR152##

The compound having the structure: ##STR153## may, in the alternative,be etherified by means of etherification reactions such as by means ofthe reaction of the compound having the structure: ##STR154## withdimethyl sulfate subsequent to reaction with base according to thereactions: ##STR155## wherein M₁ represents alkali metal such as sodium,potassium or lithium. In the alternative, the etherification reactionswhich can be utilized involve the use of isobutylene and methyl tertiarybutylether according to the reaction: ##STR156## wherein byproducts areformed, that is, the compounds having the structures: ##STR157##

The compound having the structure: ##STR158## may also be acylated aswith formic acid according to the reaction: ##STR159## or aceticanhydride according to the reaction: ##STR160## or the compound havingthe structure: ##STR161## may be first hydrogenated according to thereaction: ##STR162## and that resulting hydrogenation product may beacylated according to the reaction, for example: ##STR163## In thealternative, the acylation product may be hydrogenated according to thereaction: ##STR164## In general the hydrogenation reaction of thevarious adamantane derivatives having the methylene moiety are shownaccording to the reaction: ##STR165## wherein X represents one of themoieties: ##STR166##

It is interesting to note that during the etherification reactionadditional epimers of the compound having the structure: ##STR167## areformed, to wit, the compounds having the structures: ##STR168## Theadamantane derivatives of our invention have intense and substantivearomas which can be described as sandalwood, woody, patchouli, rhubarb,ginger, minty, amyris, camphoraceous, cardamon, earthy, cedarwood-like,vetiver, peppery, grapefruit peel-like, rose-like, ambery, spicy, gingerroot, rosemary, piney, chrysanthemum-like, green and fir balsampine-like, with sweet, amyris, camphoraceous, patchouli, woody, piney,cedarwood, sandalwood, herbaceous, incense, olibanum, vetiver,grapefruit peel-like, floral, sweet pea, rose, peony, fruit, earlymorning forest path, green, ginger root and amber topnotes. Table Ibelow sets forth the summary of the particular compounds and theiraromas:

                  TABLE I                                                         ______________________________________                                        Composition of Matter                                                                        Perfumery Properties                                           ______________________________________                                        The compound having                                                                          A sandalwood, woody,                                           the structure: patchouli, rhubarb, ginger, minty                               ##STR169##    and amyris aroma with amyris, camphoraceous, patchouli,                       woody, and piney topnotes.                                     produced according to                                                         Example III, bulked                                                           fractions 6-9.                                                                The compound having                                                                          A camphoraceous, ginger                                        the structure: cardamon and woody aroma                                        ##STR170##    profile.                                                       produced according to                                                         Example IIIA.                                                                 The compound having                                                                          A cedarwood-like, sandalwood-                                  the structure: like, camphoraceous, woody,                                     ##STR171##    minty and earthy aroma with cedarwood,sandalwood, patchouli                   , camphoraceous, herbaceous, incense and olibanum                             topnotes.                                                      prepared according to                                                         Example IV, bulked                                                            fractions 8-18.                                                               The compound having                                                                          A cedarwood-like, patchouli,                                   the structure: vetiver, peppery, grapefruit                                    ##STR172##    peel-like and camphoraceous aroma with vetiver and                            grapefruit peel-like topnotes.                                 prepared according                                                            to Example V(B),                                                              bulked fractions 7-9                                                          The compound having                                                                          A woody, rose-like and                                         the structure: peony-like aroma with floral,                                   ##STR173##    sweet pea, rose and peony topnotes.                            prepared according to                                                         Example VI, bulked                                                            fractions 10-16.                                                              The compound having                                                                          An ambery, woody and                                           the structure: cedarwood-like aroma with                                       ##STR174##    fruity and woody topnotes.                                     prepared according to                                                         Example VI, bulked                                                            fractions 5-19.                                                               The compound having                                                                          A camphoraceous aroma with                                     the structure: early morning forest path,                                      ##STR175##    green, piney, woody and camphoraceous topnotes.                prepared according to                                                         Example VII.                                                                  The compound having                                                                          A spicy, ginger root,                                          the structure: rosemary and camphoraceous                                      ##STR176##    aroma with green, woody and ginger root topnotes.              prepared according to                                                         Example X, bulked                                                             fractions 4 and 5.                                                            The compound having                                                                          A woody, ambery, vetiver,                                      the structure: cedarwood, piney and                                            ##STR177##    chrysanthemum-like aroma with woody, amber and olibanum                       topnotes.                                                      prepared according to                                                         Example XI, bulked                                                            fractions 5-9.                                                                The compound having                                                                          A woody, amber, vetvier,                                       the structure: cedarwood, piney and                                            ##STR178##    chrysanthemum-like aroma with woody, amber and olibanum                       topnotes.                                                      prepared according to                                                         Example XIII, bulked                                                          fractions 2-18.                                                               The mixture of compounds                                                                     A green, woody and fir                                         having the structures:                                                                       balsam-like aroma profile.                                      ##STR179##                                                                    ##STR180##                                                                    ##STR181##                                                                   and                                                                            ##STR182##                                                                   prepared according to                                                         Example XIV, fraction 6.                                                      The mixture of compounds                                                                     A camphoraceous aroma with sweet                               having the structures:                                                                       camphoraceous topnotes.                                         ##STR183##                                                                    ##STR184##                                                                    ##STR185##                                                                    ##STR186##                                                                    ##STR187##                                                                   and                                                                            ##STR188##                                                                   prepared according to                                                         Example XV.                                                                   The compound having                                                                          A fresh, camphoraceous, sage-                                  the structure: like and woody aroma profile                                    ##STR189##    with camphoraceous and woody topnotes.                         bulked fractions 4-6                                                          produced according                                                            to Example XII.                                                               The compound having                                                                          A natural, fresh pine, forest                                  the structure: aroma profile.                                                  ##STR190##                                                                   prepared according                                                            to Example XVI.                                                               ______________________________________                                    

DETAILED DESCRIPTION OF THE INVENTION

In carrying the reaction: ##STR191## the reaction may take place in thepresence of base; but must take place in the absence of acid.Accordingly, the reaction can be written: ##STR192## and can take placein the presence of sodium bicarbonate, sodium carbonate, potassiumbicarbonate, potassium carbonate or disodium acid phosphate in theabsence of solvent.

The temperature of reaction may be in the range of from about 130° C. upto about 250° C. with a preferred temperature of 210°-230° C. Thereaction pressure may vary from about 0.5 up to about 10 atmosphereswith a preferred reaction pressure of about 1 atmosphere. The reactionmechanism is shown, thusly: ##STR193##

At the end of the reaction, the reaction product is distilled by meansof fractional distillation (e.g., at a vapor temperature of 128°-133° C.and a pressure of 5-12 mm/Hg.).

The compound having the structure: ##STR194## produced in this fashionis actually in the form of two isomers having the structures: ##STR195##As will be shown, infra, the mixture of these two compounds is furtherempimerized to the compounds having the structures: ##STR196##

The resulting compound can then, if desired, be further reacted with areducing agent such as hydrogen whereby the methylene double bond isreduced according to the reaction: ##STR197## The reaction may becarried out in the presence of an inert solvent such as isopropylalcohol but must be carried out in the presence of a hydrogenationcatalyst, for example, Raney nickel or palladium suspended on carbon orpalladium suspended on calcium carbonate, for example, 5% palladium oncalcium carbonate. The reaction temperature may range from about 80° C.up to about 150° C. and the reaction pressure may range from about 80psig up to about 150 psig. At the end of the reaction, the reaction massis filtered, the solvent is evaporated and the reaction product isfractionally distilled.

The compound having the structure: ##STR198## or the hydrogenatedcompound thus produced having the structure: ##STR199## may beesterified, etherified or oxized.

The esterification reaction, to wit: ##STR200## takes place wherein thedashed line represents a carbon-carbon single bond or a carbon-carbondouble bond and R₃ are the same or different hydrogen or lower alkylwith the proviso that R₃ and R₃ ' are not both hydrogen. In addition,the formate ester having the structure: ##STR201## for example, can beproduced by means of reaction of formic acid with acetic anhydrideaccording to the reaction: ##STR202## In fact, the reaction may takeplace at a temperature in the range of from about 10° up to about 40° C.in the presence of an acid catalyst such as a sulfuric acid catalyst ora hydrochloric acid. Other esterification reagents include aceticanhydride which reacts with the compound having the structure:##STR203## according to the reaction: ##STR204## or propionic acidanhydride which reacts with the compound having the structure:##STR205## according to the reaction: ##STR206##

The oxidation reaction can be carried out to form a compound having thestructure: ##STR207## or it can be carried out to form a compound havingthe structure: ##STR208## In carrying out the reaction: ##STR209## atemperature of from about 0° up to about 250° C. can be used. Thereaction can be carried out in the presence of any chromic oxidizingagent, for example, "Collins" reagent which is chromium trioxide inmethylene dichloride or it can be carried out in the presence ofpyridinium dichromate or pyridinum chlorochromate at temperatues in therange of 0° to 40° C. The reaction can also be carried out in thepresence of a copper chromite catalyst at a temperature in the range of200°-220° C. The reaction may be carried from about 0.8 up to about 2atmospheres with 1 atmosphere pressure being preferred.

The etherification reactions, to wit: ##STR210## or the sequence:##STR211## are carried out as follows:

With respect to the reaction: ##STR212## the reaction can be carried outin the presence of any mineral acid, e.g., hydrochloric acid, sulfuricacid or phosphoric acid. The reaction is carried out using isobutylenein admixture with methyl tertiary butylether with a mole ratio ofisobutylene:methyl tertiary butylether ranging from about 0.5:1.5 up toabout 1.5:0.5. The reaction temperature may vary from about 35° up toabout 50° C. The reaction time may vary from about 5 hours up to about15 hours. With this particular reaction, various byproducts are formedhaving the structures, to wit: ##STR213## in addition to the compoundhaving the structure: ##STR214##

With respect to the reaction sequence: ##STR215## whereby the compoundhaving the structure: ##STR216## is formed, the first reaction, to wit:##STR217## takes place in the presence of a strong base such as sodiumhydroxide, lithium hydroxide or potassium hydroxide at a temperature inthe range of from about 10° up to about 40° C. In the alternativehowever the reaction may take place using sodium hydride or sodium inplace of the alkali metal hydroxide in order to form the compound havingthe structure: ##STR218## where M₁ is alkali metal. The resultingproduct having the structure: ##STR219## is then reacted with dimethylsulphate at a temperature in the range of 40°-80° C. with a mole ratioof dimethyl sulphate:compound having the structure: ##STR220## beingfrom about 1:1 up to about 1.2:1 according to the reaction: ##STR221##

The resultant oxidized compounds, e.g., ketones, for example, the ketonehaving the structure: ##STR222## may be further reacted to form tertiaryalcohols as with alkyl lithium and lower alkyl grignard reagentsaccording to the reaction sequence: ##STR223## wherein the dashed linerepresents a carbon-carbon single bond or a carbon-carbon double bond;and wherein M represents Li, MgBr, MgCl or MgI and R₂ represents loweralkyl. In the alternative R₂ could also represent lower alkenyl or loweralkynyl, or aryl or aralkyl or alkaryl. The conditions of this reactionare as set forth in Hallden-Aberton, J. Org. Chem., Volume 46, No. 3,1981, pages 538-546 the disclosure of which is incorporated herein byreference. Such conditions are also set forth in U.S. Pat. No. 4,439,354at column 22, 23 and 24 the disclosure of which is incorporated hereinby reference.

The resulting compound, for example, the compound having the structure:##STR224## may be esterified according to the reaction, for example:##STR225## or, for example: ##STR226## according to esterificationconditions as set forth at column 21 of U.S. Pat. No. 4,439,345 thespecification of which is incorporated herein by reference. In addition,the compound having the structure, for example: ##STR227## can beetherified forming, for example, the methylether by first reacting thecompound with sodium and then reacting the resulting sodiumorganometallic compound with methyliodide in order to form themethylether. The conditions of the etherification are set forth atcolumns 20 and 21 of U.S. Pat. No. 4,439,345 the specification of whichis incorporated herein by reference.

The adamantane derivatives of our invention having an alkylidenesubstituent at the "4" position of the adamantane ring which is:##STR228## for example, the compound having the structure: ##STR229## orthe compound having the structure: ##STR230## or the compound having thestructure: ##STR231## or the compound having the structure: ##STR232##may be reacted via an "oxo" reaction shown, generically as follows:##STR233## wherein X has the structure: ##STR234## and wherein R₁represents hydrogen, lower alkyl or lower acyl and wherein R₂ representshydrogen or lower alkyl. Thus, for example, when the compound having thestructure: ##STR235## is reacted with carbon monoxide and hydrogen, thefollowing reaction takes place: ##STR236## wherein compounds shown bythe structures: ##STR237## are indicative of one or more isomers each asindicated by the wavy line showing the methyl moiety bonded at the "9"position of the adamantane moiety. The reaction of the adamantanederivatives having the alkylidene substitution at the "4" position withcarbon monoxide and hydrogen, the "oxo" reaction is carried out in thepresence of a "oxo reaction catalyst" such as rhodium, Co₂ (CO)₈, ororganophosphorous polydentate ligand such as those described in EuropeanPublished Application 33,554 published on Aug. 12, 1981, thespecification of which is incorporated herein by reference. Examples ofwhich are: ##STR238## at pressures of from about 3 atmospheres up toabout 1,000 atmospheres and at temperatures in the range of from about30° C. up to about 150° C. Preferably when using a rhodium catlayst, thetemperature of reaction is between 70° and 110° C.; when using a Co₂(CO)₈ catalyst, the temperature is between 110° and 120° C.; and whenusing a ligand such as those exemplified in European PublishedApplication 33,544, the specification of which is incorporated herein byreference, the temperature may vary from 95 C. up to 120° C. as is setforth in the following table:

                  TABLE A                                                         ______________________________________                                        Ligand          Reaction Temperature                                          ______________________________________                                        φ.sub.2 P(CH.sub.2).sub.2 Pφ.sub.2                                                    95-120° C.                                              ##STR239##     120° C.                                                 ##STR240##     120° C.                                                φ.sub.2 PCHCHPφ.sub.2                                                                 120° C.                                                 ##STR241##      95° C.                                                φ.sub.2 P(CH.sub.2).sub.4 Pφ.sub.2                                                     95° C.                                                φ.sub.2 P(CH.sub.2).sub.3 Pφ.sub.2                                                     95° C.                                                Pφ.sub.3    120° C.                                                φ.sub.2 P(CH.sub.2).sub.10 Pφ.sub.2                                                   120° C.                                                φ.sub.2 PCH.sub.2 Pφ.sub.2                                                            120° C.                                                (CH.sub.3).sub.2 P(CH.sub.2).sub.2 P(CH.sub.3).sub.2                                          120° C.                                                ______________________________________                                    

The resulting reaction product is then separated as by fractionaldistillation thereby yielding a mixtures of compounds including, but notlimited to aldehydes.

The resulting mixtures and/or compounds (if further separated as bypreparative GLC) may be used "as is" for their organoleptic propertiesor they may be further reacted by oxidation or reduction techniques,e.g., as by hydrogenation using a hydrogenation catalyst or by oxidationusing a chromium oxidation catalyst. Furthermore, thealdehyde-containing compositions may be further reacted as by reductionwith an alkali metal or alkali metal hydride such as sodium borohydride,lithium aluminum hydride and the like. When a reaction takes place usinga reducing agent such as sodium borohydride or lithium aluminum hydride,the mole ratio of aldehyde:alkali metal hydride is in the range of fromabout 1:1 up to about 4:1 with a preferred mole ratio of aldehyde:alkalimetal hydride being about 3:1. The reaction takes place at refluxconditions in a solvent which will permit reflux conditions atatmospheric pressure. The reaction takes place in the presence of aninert solvent, that is, a solvent inert to the reactants and thereaction product and one which will permit a reflux temperature atatmospheric pressure in the range of from about 80° up to about 100° C.A preferred solvent is isopropyl alcohol. The concentration of aldehydein the reaction mass may vary from about 5 moles per liter up to about15 moles per liter with a concentration of aldehyde in the reaction mass(initially) being about 10 moles per liter. The concentration of alkalimetal hydride in the reaction mass may very from about 2 moles per literup to about 6 moles per liter with a preferred concentration of alkalimetal hydride in the reaction mass being about 4 moles per liter.

The adamantane derivatives of our invention can be used to contributepowerful, long-lasting, sandalwood, woody, patchouli, rhubarb, ginger,minty, amyris, camphoraceous, cardamon, earthy, cedarwood-like, vetiver,peppery, grapefruit peel-like, rose-like, ambery, spicy, ginger root,rosemary, piney, chrysanthemum-like, green and fir balsam pine-likearomas, with sweet, amyris, camphoraceous, patchouli, woody, piney,cedarwood, sandalwood, herbaceous, incense, olibanum, vetiver,grapefruit peel-like, floral, sweet pea, rose, peony, fruity, earlymorning forest path, green, ginger root and amber topnotes to perfumecompositions, perfumed articles, colognes, deodorizing articles,deodorizing compositions and malodor maskants. Examples of perfumedarticles are anionic, cationic, nonionic and zwitterionic detergents,drier-added fabric softener compositions and drier-added fabric softenerarticles as well as hair preparations. As olfactory agents, theadamantane derivatives of our invention can be formulated into or usedas components of a "perfume composition" or can be used as components ofa "perfumed article" or the perfume composition may be added to perfumedarticles.

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols (other than thehydroxy-substituted adamantane derivatives of our invention); aldehydes(other than the oxo reaction products of our invention); ketones, (otherthan the keto-substituted adamantane derivatives of our invention),nitriles, ethers (other than the alkoxy-substituted adamantanederivatives of our invention), lactones, natural essential oils,synthetic essential oils, synthetic essential oils and frequentlyhydrocarbons which are admixed so tha the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain (a) the main note or the "bouquet"or foundation stone of the composition; (b) modifiers which round offand accompany the main note; (c) fixatives which include odoroussubstances which lend a particular note to th perfume throughout allstages of evaporation and substances which retard evaportation; and (d)topnotes which are usually low boiling, fresh smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, the individual adamantane derivatives of thisinvention or mixtures thereof can be used to alter the aromacharacteristics of a perfume composition, for example, by highlightingor moderating the olfactory reaction contributed by another ingredientin the composition.

The amount of the adamantane derivative(s) of this invention which willbe effective in perfume compositions, depends on many factors includingthe other ingredients, their amounts, and the effects which are desired.It has been found that perfume compositions containing as little as 0.5%of one or more of the adamantane derivatives of our invention or evenless can be used to impart interesting sandalwood, woody, patchouli,rhubarb, ginger, minty, amyris, camphoraceous, cardamon, earthy,cedarwood-like, vetiver, peppery, grapefruit peel-like, rose-like,ambery, spicy, ginger root, rosemary, piney, chrysanthemum-like, greenand fir balsam pine-like aromas, with sweet, amyris, camphoraceous,patchouli, woody, piney, cedarwood, sandalwood, herbaceous, incense,olibanum, vetiver, grapefruit peel-like, floral, sweet pea, rose, peony,fruit, early morning forest path, green, ginger root and amber topnotesto soaps, liquid and solid anionic, cationic, nonionic and zwitterionicdetergents, cosmetic powders, liquid and solid fabric softeners, opticalbrightener compositions, perfumed polymers and other products. Theamount employed can range up to 50% or higher and will depend onconsiderations of cost, nature of the end product and the effect desiredon the finished product and the particular fragrance sought.

The adamantane derivatives of this invention can be used alone or aperfume composition as an olfactory component in detergents and soaps,space odorants and deodorants; colognes, toilet waters, bath salts, hairpreparations, such as lacquers, brilliantines, pomades and shampoos;cosmetic preparations such as creams, deodorants, hand lotions and sunscreens; powders such as talcs, dusting powders, face powders and thelike. When used as an olfactory component of a perfumed article, aslittle as 0.01% of one or more of the adamantane derivatives of ourinvention will suffice to impart interesting, long-lasting, sharp,sandalwood, woody, patchouli, rhubarb, ginger, minty, amyris,camphoraceous, cardamon, earthy, cedarwood-like, vetiver, peppery,grapefruit peel-like, rose-like, ambery, spicy, ginger root, rosemary,piney, chrysanthemum-like, green and fir balsam pine-like aromas, withsweet, amyris, camphoraceous, patchouli, woody, piney, cedarwood,sandalwood, herbaceous, incense, olibanum, vetiver, grapefruitpeel-like, floral, sweet pea, rose, peony, fruit, early morning forestpath, green, ginger root and amber topnotes. Generally, no more than0.5% is required.

In addition, the perfume composition can contain a vehicle or carrierfor the adamantane derivative(s) taken alone or taken together withother ingredients. The vehicle can be a liquid such as an alcohol suchas ethanol, a glycol such as propylene glycol or the like. The carriercan be an absorbent solid such as gum, (e.g., gum arabic, guar gum andxanthan gum) or components for encapsulating the composition such asgelatin which can be used to form a capsule wall surrounding the perfumeoil as by means of coacervation.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor includingmethods of making the same which overcome problems heretoforeencountered in the creation or enhancement of specific desired sweet,oriental notes. Such notes both prior to and on smoking in both the mainstream and the side stream, may now be readily controlled and maintainedat the desired uniform level regardless of variations in the tobaccocomponents of the blend; or the nature of the filter used in conjunctionwith the smoking tobacco article.

This invention further provides improved tobacco additives for materialsused in the fabrication of tobacco articles (particularly smokingtobacco articles) and methods whereby desirable sweet, oriental notesmay be imparted to smoking tobacco products and may be readily variedand controlled to produce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient(s), oneor more of the adamantane derivatives of our invention.

In addition to the adamantane derivatives of our invention, otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in admixture withone or more adamantane derivatives of our invention:

I. SYNTHETIC MATERIALS

Beta-methylcinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexen-1-ol;

2-Methyl-5-isopropyl-1-3-nonadiene-8-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,69a-tetramethylnaphtho(2,1-B)-furan;

4-Judrpxujexempoc acid, gamma-lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

II. NATURAL OILS

Celery seed oil;

Coffee extract;

Bergamot oil;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or more of theadamantane derivatives of our invention and, if desired, one or more ofthe above-indicated additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapperor to a filter which is part of the smoking article. The smoking tobaccomaterial may be shredded, cured, cased or blended tobacco material orreconstituted tobacco material or tobacco substituted (e.g., lettuceleaves) or mixtures thereof. The proportions of flavoring additives maybe varied in accordance with taste, but insofar as enhancement or theimparting of sweet, oriental, "Turkish" like notes prior to and onsmoking, in both the main stream and the side stream, we have found thatsatisfactory results are obtained if the proportion by weight of the sumtotal of adamantane derivatives to smoking tobacco material is between50 ppm and 1500 ppm (0.005%-0.15%) of the active ingredients to thesmoking tobacco material. We have further found that satisfactoryresults are obtained if the proportions by weight of the sum total ofadamantane derivatives used to flavoring material is between 0.05:1 and0.50:1. volatile organic solvents, and the resulting solution may eitherbe sprayed on a cured, cased and blended blended tobacco material; orthe tobacco material or filter may be dipped into such solution. Undercertain circumstances a solution of one or more of the adamantanederivatives of our invention taken alone or taken further together withother flavoring additives are set forth, supra, may be applied by meansof a suitable applicator such as a brush or roller on the paper or leafwrapper for the smoking product, or it may be applied to the filter byeither spraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated, and the thus-treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have one or more of theadamantane derivatives of our invention in excess if the amounts ofconcentrations above indicated so that when blended with other tobaccos,the final product will have the percentage within the indicated range.

While our invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othertobacco products formed from sheeted tobacco dust or fines may also beused. As stated, supra, one or more of the adamantane derivatives of ourinvention can be incorporated with materials such as filter tipmaterials, seam paste, packaging materials and the like which are usedalong with the tobacco to form a product adpated for smoking.Furthermore, the adamantane derivatives of our invention can be added tocertain tobacco substitutes of natural or synthetic origin (e.g., driedlettuce leaves) and, accordingly, by the term "tobacco" as usedthroughout this specification is meant any composition intended forhuman consumption, by smoking or otherwise, whether composed of toaccoplant parts or substituted materials or both.

It will thus be apparent that the adamantane derivatives of ourinvention can be utilized to alter, modify, augment or enhance sensoryproperties, particularly organoleptic properties, such as flavor(s)and/or fragrance(s) of a wide variety of consumable materials.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% alcoholsolution of the compound having the structure: ##STR242## in an amountto provide a tobacco composition containing 800 ppm by weight of thecompound having the structure: ##STR243## on a dry basis. Thereafter thealcohol is removed by evaporation and the tobacco is manufactured intocigarettes by the usual techniques. The cigarette, when treated asindicated has a desired and pleasant aroma which is detectable in themain stream and in the side stream when the cigarette is smoked. Thearoma as described as being oriental, natural Turkish tobacco-like withpleasant and long-lasting cigar box-like nuances.

Our invention also relates to the utilization of controlled releasetechnology for the controlled release of perfumes into gaseousenvironments; odor maskants and deodorizing agents into gaseousenvironments; and tobacco aromatizing and flavors into smoking articlefilters from polymers such as mixtures of epsilon polycaprolactonepolymers and polyethylene which poly epsilon caprolactone polymers aredefined according to at least one of the structures: ##STR244## wherein"n" is from about 50 up to about 1,200 with the proviso that the average"n" n the system varies from about 150 up to about 700 according to themathematical statement:

    [700≧n≧150]

with the term n being the average number of repeating monomeric unitsfor the epsilon polycaprolactone polymer. The perfumed or flavoredmaterial's release rate from such polymer mixture is close to "zeroorder". As a general rule, the release rate in a polymeric matrix isproportional to t^(-1/2) until about 60% of the functional fluid (e.g.,the adamantane derivative of our invention) is released from thepolymeric matrix. The release rate thereafter is related exponentiallyto time as a general rule according to the equation: ##EQU1## wherein k₁and k₂ are constants. According to Kydonieus, "Controlled ReleaseTechnologies: Methods, Theory, and Applications", the amount of perfumecomposition released is proportional to time as long as theconcentration of perfume or flavor material present, e.g., theadamantane derivatives of our invention is higher than the solubility ofthe agent in the matrix. Thus, such dispersed systems are similar to thedissolved systems except that instead of a decreased release rate after60% of the perfume or flavor material has been emitted, the relationshipholds almost over the complete release curve. Kydonieus further states,that if one assumes that the release of functional fluid by diffusion isnegligible in monolithic erodible systems, the speed of erosion willcontrol the release rate and release by erosion by asurface-area-dependent phenomenon, the release is constant (zero order)as long as the surface area does not change during the erosion process.This is the case with the polymers containing the adamantane derivativesof our invention.

The polyepsilon caprolactone polymers useful in practicing our inventionare more specifically described in the brochure of the Union CarbideCorporation, 270 Park Avenue, New York, N.Y. 10017, entitled "NEWPOLYCAPROLACTONE THERMOPLASTIC POLYMES PCL-300 AND PCL-700"(incorporated herein by reference) the polyepsilon caprolactone polymersare composed of a repeating sequence of non-polar methylene groups andrelatively polar ester groups. The average number of repeating monomericunits varies between 150 and 700 depending on the particular "PCL"number. Thus, regarding PCL-300 the average number of repeatingmonomeric units is about 300. Regarding PCL-700, the average number ofrepeating monomeric units is 700.

The polyepsilon caprolactone homopolymers which are ultimately taken inadmixture with such materials as polyethylene useful in the practice ofour invention may also be stabilized using stabilizers as defined inU.S. Letters Patent No. 4,360,682 issued on Nov. 23, 1982, thespecification of which is incorporated herein by reference. Thestabilizing materials which stabilize the polyepsilon caprolactoneuseful in conjunction with our invention against discoloration aredihydroxybenzenes such as hydroquinone or compounds having the formula:##STR245## in which R₁ is alkyl of from 1 to 8 carbon atoms, and R₂ ishydrogen or alkyl of 1 to 8 carbon atoms. It is preferable to have suchstabilizer in the polyepsilon caprolactone homopolymer in an amount offrom about 100 to 500 ppm. Such stabilizers do not interfer with thefunctional fluids dissolved and/or adsorbed into the polymeric matrix.

The method of incorporating the adamantane derivatives of our inventionor perfume compositions containing same into the polymers may beaccording to the technique of U.S. Letters Patent No. 3,505,432 issuedon Apr. 7, 1970 (the specification for which is incorporated herein byreference) or U.S. Letters Patent No. 4,274,498 issued on Jan. 27, 1981,the disclosure of which is incorporated by reference herein.

Thus, for example, a first amount of liquid polyethylene-polyepsiloncaprolactone plymer mixture (50:50) is mixed with one or more of theadamantane derivatives of our invention. Drops are formed from themixture and the drops are solidified. The solidified drops are thenmelted, if desired, with a second amount of unscented low densitypolyethylene, for example, or polypropylene, for example. Usually, butnot necessarily, the second amount of polymer is larger than the firstamount. The resulting mixture thus obtained is solidified subsequent toor prior to ultimate casting into a utilitarian shape.

Thus, in accordance with one aspect of our invention the imparting ofscent is effected in two stages. In a first stage, a 50:50(weight:weight) polyepsilon caprolactone, e.g., PCL-700: polyethylene inmolten form is admixed with a high percentage of one or more of theadamantane derivatives of our invention, e.g., the compound having thestructure: ##STR246## and the mixture is solidified in the form ofpellets or beads. These pellets or beads thus contain a high percentageof adamantanes (e.g., up to 45% by weight of the entire mixture) and maybe used as "master pellets" which thereafter, in a second stage, ifdesired, may be admixed and liquified with additional polymers such asadditional polyethylene or mixtures of polyethylene and polyepsiloncaprolactone in an unscented state, or unscented polypropylene. Inaddition, additional polymers or copolymers may be used, for example,copolymers specified and described in United Kingdom PatentSpecification No. 1,589,201 published on May 7, 1981, the specificationfor which is incorporated by reference herein.

In accordance with the present invention at least one of the adamantanederivatives of our invention is added to the polymer in a large closedcontaier or drum which is maintained under controlled temperatureconditions while the polymer in a melted condition is mixed with atleast one of the adamantane derivatives under agitation.

In order that the perfume or flavor be added uniformly to the polymer,the temperature of the melt is constantly controlled during the process.The polymer-perfume mixture is then directed through an elongatedconduit or pipe element having a plurality of orifices adjacent to thelower most portion thereof. The polymer enriched by at least one of theadamantane derivatives of our invention is permitted to drip through theorifices onto a continuously moving, cooled conveyor upon which thepolymer containing at least one of the adamantane derivatives of ourinvention solidifies into small size pellets with the perfume and/orflavor imprisoned therein. The apparatus useful in conjunction with thisprocess advantageously includes a conveyor of a material which will notadhere to the polymer which contains at least one of the adamantanederivatives of our invention.

In order that the droplets form into uniform pellets or beads, theconveyor is continuously washed with a liquid such as water to maintainthe surface relatively cool. The pellets are delivered by the conveyorinto a container and packaged for shipment or for further incorporationito articles of manufacture, e.g., garbage bags (using the deodorizationquality of the adamantane derivatives of our invention) or tobaccofilters (using the tobacco flavoring or flavor enhancement properties ofthe adamantane derivatives of our invention).

The following Examples A, I and II set forth the preparation of theprecursors of the adamantane derivatives of our invention. ExamplesIII-XVI set forth preparation of the adamantane derivative compositionsof our invention. Examples XVIII, et seq. set forth the organolepticuses of the adamantane derivatives of our invention prepared accordingto Examples III-XVI.

The following Examples III, et seq. serve to illustrate our invention,and this invention is to be considered restricted thereto only asindicated in the appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE A PREPARATION OF 3(4-METHYL-3-CYCLOHEXEN-1-YL)BUTANAL ##STR247##PART I PRODUCTION OF OXO REACTION CATALYST

150 ml Methanol is admixed with 36 grams of triphenyl phosphine, 1.2grams of RhCl₃.H₂ O and 2.4 grams of sodium bicarbonate. The resultingmixture is heated at reflux for a period of one hour and then cooled.

PART II OXO REACTION

Into an autoclave rated for 1000 psig pressure and containing heatingelements is placed 2583.7 grams (18.99 moles) of D-limonene having thestructure: ##STR248## and the oxo reaction catalyst prepared in Part I,supra. The autoclave is sealed and heated to 110° C. and pressurized to600 psig using a 50:50 mole:mole mixture of carbon monoxide andhydrogen. The autoclave pressure is then maintained at 600 psig and 110°C. for a period of eleven hours.

At the end of the eleven hour period, the autoclave is depressurized,the contents are cooled and the autoclave is opened. The contents of theautoclave are then distilled using a 2" splash column yielding thefollowing fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight of                                  Fraction  Temp    Temp      mm/Hg. Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (Grams)                                    ______________________________________                                        1         68/82   88/89     8/7    102.5                                      2         83       91       6       39.7                                      3         96      104       5      196.1                                      4         97      104       5      195.8                                      5         99      115       5      2318.3                                     6         93      119       5      107.6                                      7         80      125       4       10.0                                      ______________________________________                                    

The resulting product, having the structure: ##STR249## is then utilizedin the following Example I.

FIG. A is the GLC profile for the crude reaction product prior todistillation. The peak indicated by reference numeral 5 is the peak forthe compound having the structure: ##STR250## (Conditions: K-20M columnprogrammed at 130°-220° C. at 8° C. per minute.

EXAMPLE I PREPARATION OF 2-METHYLENE-3-(4-METHYL-3-CYCLOHEXENYL)BUTANAL##STR251##

Into a 3 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle and nitrogen blanket apparatus isplaced 613 grams (7.546 moles) of formaldehyde. 44.3 Grams (0.34 moles)of dibutyl amine is then added to the reaction mass. Over a period of0.5 hours while maintaining the reaction mass at room temperature, 22.1grams (0.37 moles) of acetic acid is added dropwise to the reactionmass.

The reaction mass, with stirring, is heated to 90°-95° C.

While maintaining the reaction mass at 90°-95° C. over a period of 0.5hours, 1140 grams (6.86 moles) of the compound having the structure:##STR252## is added to the reaction mass.

The reaction mass is then refluxed for a period of 30 hours at 90°-95°C.

At the end of the 30 hour period, the reaction mass is cooled and washedwith:

(a) water;

(b) 5% aqueous sodium carbonate; and

(c) saturated sodium chloride solution.

686.5 Grams of the compound having the structure: ##STR253## areproduced (percent weight yield: 60.2%).

The resulting washed product is then fractionally distilled on a 2"splash column yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         /75     /96       2.2     92.0                                      2         84      106       2.0    394.8                                      3         32       12       2.0    665.0                                      ______________________________________                                    

Fractions 2, 3, 4, 5, and 6 are bulked and redistilled on a 1" Goodloecolumn yielding the following fractions:

    ______________________________________                                                Vapor   Liquid   Vacuum        Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg. Reflux Fraction                               No      (°C.)                                                                          (°C.)                                                                           Pressure                                                                             Ratio  (Grams)                                ______________________________________                                        1       /70     /91      1.4    12:1   29                                     2       74       90      1.5    12:1   26                                     3       83      101      2.3    9:1    58                                     4       82      101      2.1    9:1    60                                     5       83      101      2.2    9:1    79                                     6       82      101      1.6    9:1    78                                     7       85      103      1.7    7:1    92                                     8       85      103      1.7    7:1    56                                     9       79      104      1.5    7:1    100                                    10      80      107      1.6    7:1    101                                    11      80      119      1.6    7:1    81                                     12      80      165      1.6    7:1    35                                     ______________________________________                                    

FIG. 1 is the GLC profile for the crude reaction product. The peakindicated by reference numeral 10 is the peak for the compound havingthe structure: ##STR254## (Conditions: K-20 M column programmed at130°-220° C. at 8° C. per minute).

FIG. 2 is a cross scan GC profile for the crude reaction product. Thepeak indicated by reference numeral 21 is the peak for the compoundhaving the structure: ##STR255## The peaks indicated by referencenumerals 22 and 23 are the peaks for byproducts of the reaction havingthe structure: ##STR256## wherein in each of the compounds one of thedashed lines is a carbon-carbon double bond and the other of the dashedlines is a carbon-carbon single bond and each of the compounds isdifferent from the other.

FIG. 3 is the NMR spectrum for the compound having the structure:##STR257## (CFCl₃ solvent) at 100 MHz.

EXAMPLE II PREPARATION OF 2-METHYLENE-3-(4-METHYL-3-CYCLOHEXENYL)BUTANAL##STR258##

Into a 3 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle are placed 1410 grams (17.35 moles)of formaldehyde and 101.3 grams (0.78 moles) of dibutyl amine. Over aperiod of 15 minutes, 82.8 grams (1.38 moles) of acetic acid is added tothe reaction mass. The reaction mass is then heated to 90° C. and over aperiod of 35 minutes 2640 grams (15.9 moles) of the compound having thestructure: ##STR259## is added to the reaction mass with stirring. Thereaction mass is maintained with stirring at 90° C. for a period of 2hours. At the end of the 2 hour period, the reaction mass is extractedwith one volume of toluene. The toluene extract is then washed asfollows:

(a) one volume of 5% phosphoric acid;

(b) one volume of water; and

(c) one volume of saturated sodium bicarbonate.

The reaction mass is then distilled on a 2" splash column yielding thefollowing fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         /43     /80       3.00/2.4                                          2         103     113       0.5    356                                        3         118     125       1.7    869                                        4         120     127       2.9    849                                        5         129     170       1.8    771                                        6          95     203       1.7    153                                        ______________________________________                                    

The weight yield is 93% of product having the structure: ##STR260##

FIG. 4 is the GLC profile for fraction 4 of the foregoing distillation(Conditions: K-20 M column programmed at 130°-220° C. at 8° C. perminute). The peak indicated by reference numeral 41 is the peak for thecompound having the is the peak for the compound having the structure:##STR261##

EXAMPLE III PREPARATION OF 2-HYDROXY-4-METHYLENE-8-METHYLTRICYCLO[3.3.1.1.³,7 ]DECANE (ALSO NAMED4-METHYL-8-METHYLENE-2-ADAMANTOL) ##STR262##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle are placed 100 grams PRIMOL® and 26grams of sodium bicarbonate. The reaction mass is heated to 78° C. Whilemaintaining the reaction mass at 78° C. over a period of one hour, 835grams of the compound having the structure: ##STR263## preparedaccording to Example II is added to the reaction vessel. During theaddition the reaction vessel is heated up slowly to 210° C. Whilemaintaining the reaction mass at 200°-210° C. over a period of 2.5 hoursan additional 1665 grams of the compound having the structure:##STR264## is added to the reaction mass with stirring. The reactionmass is then stirred at a temperature in the range of 208°-212° C. for aperiod of two hours.

The reaction mass is then distilled on a packed column packed withRaschig Rings yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight of                                  Fraction  Temp.   Temp.     mm/Hg. Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (Grams)                                    ______________________________________                                        1          117/    135/     8.0     40                                        2         122     137       7.8    171                                        3         128     141       8.7    196                                        4         129     143       11.7   414                                        5         137     153       12.1   844                                        6         133     191       5.7    673                                        7         109     205       5.0     6                                         ______________________________________                                    

FIG. 5 is the GLC profile for the crude reaction product. The peaksindicated by reference numerals 52 and 53 are peaks indicating solvent.The peak indicated by reference numeral 51 is the peak for the reactionproduct having the structure: ##STR265## which is a mixture of isomershaving the structures: ##STR266## (Conditions: Carbowax columnprogrammed at 130°-220° C. at 8° C. per minute).

Bulked distillation fractions 6-9 have a sandalwood, woody, patchouli,rhubarb, ginger, minty and amyris aroma with amyris, camphoraceous,patchouli, woody and piney topnotes.

EXAMPLE III(A) PREPARATION OF 2-HYDROXY-4-METHYLENE-8-METHYLTRICYCLO[3.3.1.1³,7 ]DECANE (ALSO NAMED4-METHYL-8-METHYLENE-2-ADAMANTOL) ##STR267##

Into a 20 ml Parr bomb set in an oil bath is placed 10 grams of thecompound having the structure: ##STR268## 0.5 grams of Na₂ HPO₄ ; and 5grams of ETHOMEEN® C-12 (n-dodecyl-di-hydroxyethyl amine manufactured bythe Rohm And Haas & Company of Philadelphia, Pa.).

The Parr bomb is closed and the oil bath is heated to 200°-240° C. andmaintained at 200°-240° C. for a period of three hours.

At the end of the three hour period, the Parr bomb is cooled and openedand the reaction mass is analyzed.

FIG. 5A is the GLC profile for the crude reaction product. The peakindicated by FIG. 54 is the peak for one or both of the compoundsdefined according to the structure: ##STR269## wherein one of the dashedlines is a carbon-carbon double bond and the other of the dashed linesis a carbon-carbon single bond; the peaks indicated by FIGS. 56 and 57are for one or both of the compounds defined according to the structure:##STR270## wherein one of the dashed lines is a carbon-carbon doublebond and the other of the dashed lines is a carbon-carbon single and thepeak indicated by reference numeral 55 is the peak for the compounddefined according to the structure: ##STR271##

FIG. 5B is the NMR spectrum for the compound having the structure:##STR272## (a mixture of isomers having the structures: ##STR273##

FIG. 5C is the NMR spectrum for one or both of the compounds definedaccording to the structure: ##STR274## wherein one of the dashed linesis a carbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond.

The reaction product has a camphoraceous, gingery, cardamon and woodyaroma profile.

EXAMPLE IV PREPARATION OF 4-METHYLENE-8-METHYL TRICYCLO[3.3.1.1³,7]DECANYL-2-FORMATE (ALSO NAMED 8-METHYL-4-METHYLENE-2-ADMANTOL FORMATE)##STR275##

Into a 2 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle are placed 677 grams (3.8 moles) ofthe compound having the structure: ##STR276## 240 grams of formic acidand 2 grams of oxalix acid. The resulting mixture with stirring isheated to 80° C. Over a period of three hours, 530 grams of aceticanhydride is fed into the reaction mass while maintaining the reactionmass at 90°-95° C. The reaction mass is then maintained at 82°-83° C.for a period of 0.70 hours. the reaction mass is then cooled and theaqueous phase is separated from the organic phase. The aqueous phase isextracted with 100 cc of toluene and the toluene extract is combinedwith the organic phase. The organic layer is then washed as follows:

(a) one 400 ml portion of saturated sodium chloride solution;

(b) one portion of 5% aqueous sodium bicarbonate; and

(c) two portions of saturated sodium chloride.

The resulting product is then dried over anhydrous magnesium sulfate anddistilled on a 2" splash column yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight of                                  Fraction  Temp.   Temp.     mm/Hg. Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (Grams)                                    ______________________________________                                        1          55/     74/      100                                               2         60      105       270                                               3         49       83       115                                               4         52      110        65    52                                         5         45/108  128/118   70/4.5 80                                         6         97      107       1.6    150                                        7         96      104       1.4    103                                        8         95      103       1.3    82                                         9         97      107       1.2    119                                        10        108     128       1.3    84                                         11        128     190       1.6    39                                         12        128     200       1.8     8                                         ______________________________________                                    

Fractions 4-10 are bulked and redistilled on a 1"×10" Goodloe columnyielding the following fractions:

    ______________________________________                                                Vapor   Liquid   Vacuum        Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg. Reflux Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                             Ratio  (Grams)                                ______________________________________                                        1       77/56   114/133  1.5/1.4                                                                              19:1   53                                     2       92      120      1.6    9:1    17                                     3       93      114      1.6    9:1    13                                     4       97      118      1.7    4:1    18                                     5       94      119      1.5    4:1    35                                     6       95      119      1.5    4:1    27                                     7       96      116      1.66   4:1    43                                     8       96      116      1.56   4:1    42                                     9       97      116      1.75   4:1    37                                     10      97      116      1.63   4:1    52                                     11      98      117      1.60   4:1    51                                     12      96      117      1.55   4:1    42                                     13      97      118      1.60   4:1    44                                     14      97      125      1.57   4:1    40                                     15      97      138      1.51   4:1    36                                     16      98      150      1.63   4:1    20                                     17      112     180      1.77   4:1    13                                     ______________________________________                                    

FIG. 6 is the GLC profile for the crude reaction product prior todistillation containing the compound having the structure: ##STR277##(Conditions: Carbowax column programmed at 130°-220° C. at 8° C. perminute).

FIG. 7 is the NMR spectrum for the compound having the structure:##STR278##

The compound having the structure: ##STR279## has a woody,cedarwood-like, sandalwood-like, camphoraceous, minty and earthy aromaprofile with cedarwood, sandalwood, patchouli, camphoraceous,herbaceous, incense and olibanum topnotes (bulked distillation fractions8-18).

EXAMPLE V(A) PREPARATION OF 4-METHYLENE-8-METHYL-TRICYCLO[3.3.1.1³,7]DECAN-2-YL ACETATE(ALSO NAMED 8-METHYL-4-METHYLENE-2-ADAMANTOL ACETATE)##STR280##

Into a 500 ml reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle is placed 100 grams of acetic anhydride.The acetic anhydride is heated to 80° C. and over a period of 0.5 hours,71 grams of the compound having the structure: ##STR281## is added tothe acetic anhydride (dropwise). The reaction mass is then heatedbetween 78° and 80° C. for a period of five hours and is then refluxedat 115° C. for a period of four hours.

FIG. 8 is the GLC profile for the crude reaction product. The peaksindicated by reference numerals 81 and 82 are the peaks for the twoisomers of the compound having the structure: ##STR282## which twoisomers have the structures: ##STR283## (Conditions: Carbowax columnprogrammed at 130°-220° C. at 8° C. per minute).

FIG. 9 is the NMR spectrum for the compound having the structure:##STR284##

FIG. 10 is the NMR spectrum for the mixture of compounds having thestructures: ##STR285##

EXAMPLE V(B) PREPARATION OF 4-METHYLENE-8-METHYL-TRICYCLO[3.3.1.1³,7]DECAN-2-YL ACETATE(ALSO NAMED 8-METHYL-4-METHYLENE-2-ADAMANTOL ACETATE)##STR286##

Into a 1 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle are placed 180 grams of aceticanhydride. The acetic anhydride is heated to 95° C. and over a period of0.5 hours, 298 grams of the compound having the structure: ##STR287## isadded to the acetic anhydride, dropwise without refluxing. 100 Grams oftoluene is added to the reaction mass and the reaction mass is heated at97°-99° C. for a period of one hour. At the end of the one hour period,the reaction mass is distilled on a 1"×10" Goodloe column yielding thefollowing fractions:

    ______________________________________                                                Vapor   Liquid   Vacuum        Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg. Reflux Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                             Ratio  (Grams)                                ______________________________________                                        1       103/     133/    250/   1:1    183                                    2       56      109      44.0   1:1    123                                    3       78      123      2.2    4:1    38                                     4       108     138      2.6    4:1    88                                     5       102     121      2.63   4:1    30                                     6       104     123      2.76   4:1    33                                     7       98      121      2.18   4:1    30                                     8       98      120      2.14   4:1    25                                     9       98      121      2.19   4:1    24                                     10      98      125      2.10   4:1    20                                     11      97      138      2.02   4:1    19                                     12      98      180      2.09   4:1    14                                     13      95      200      4:1    4:1     5                                     ______________________________________                                    

FIG. 11 is the GLC profile for the crude reaction product containing thecompounds having the structures: ##STR288## (Conditions: Carbowax columnprogrammed at 130°-220° C. at 8° C. per minute). Bulked distillationfractions 7-9 have a cedarwood-like, patchouli, vetiver, peppery,grapefruit peel-like and camphoraceous aroma profile with woody, vetiverand grapfefruit peel-like topnotes.

EXAMPLE VI PREPARATION OF 4-METHYLENE-8-METHYL TRICYCLO[3.3.1.1³,7]DECAN-2-YL PROPIONATE (ALSO NAMED 4-METHYL-8-METHYLENE-2-ADMANTOLPROPIONATE) ##STR289##

Into a 1 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle is placed 356 grams of the compoundhaving the structure: ##STR290##

The compound having the structure: ##STR291## is heated to 80°-90° C.and over a period of one hour while maintaining the reaction mass at 88°C., 340 grams of propionic anhydride is added to the reaction mass withstirring.

The reaction mass is then maintained at 88° C. for a period of fourhours whereupon the reaction temperature is raised to 110° C. andmaintained at that temperature for a period of one hour.

The reaction mass is then distilled on a 11/2"×12" Goodloe columnyielding the following fractions:

    ______________________________________                                                Vapor   Liquid   Vacuum        Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg. Reflux Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                             Ratio  (Grams)                                ______________________________________                                         1      78/55   118/116  135/16 3:1                                            2       52     102      6.6    9:1    24                                      3       53     122      6.1    9:1    29                                      4       56     137      2.2    9:1    35                                      5      108     133      2.3    9:1    26                                      6      117     138      2.0    9:1    34                                      7      102     132      1.3    9:1    27                                      8      101     131      1.3    9:1    28                                      9      104     133      1.4    9:1    10                                     10      113     133      2.1    9:1    29                                     11      113     135      1.9    9:1    45                                     12      120     137      2.6    9:1    31                                     13      120     137      2.8           29                                     14      120     138      2.6           32                                     15      120     138       2.64         28                                     16      119     141       2.47         26                                     17      120     152       2.60         25                                     18      120     154       2.64         20                                     19      120     180       2.64         26                                     ______________________________________                                    

FIG. 12 is the GLC profile for the crude reaction product containing thecompound having the structure: ##STR292## (Conditions: Carbowax columnprogrammed at 130°-220° C. at 8° C. per minute).

FIG. 13 is the NMR spectrum for the compound having the structure:##STR293##

The compound having the structure: ##STR294## (bulked fractions 10-16has a woody, rose-like, peony-like aroma profile with floral, sweet pea,rose and peony topnotes).

When fractions 5-19 are bulked, the resulting mixture has an ambery,woody and cedarwood-like aroma profile with fruity and woody topnotes.

EXAMPLE VII PREPARATION OF 4-METHYLENE-8-METHYL TRICYCLO[3.3.1.1³,7]DECAN-2-ONE (ALSO NAMED 8-METHYL-4-METHYLENE ADAMANTONE-2) ##STR295##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle are placed 280 ml acetone and 420grams of the compound having the structure: ##STR296## The resultingmixture is cooled to 15° C. Slowly over a period of five hours a mixtureof 235 grams of chromium trioxide and 205 grams of sulfuric acid and1500 ml water is added dropwise while maintaining the reaction mass at25° C.

At the end of the five hour addition period, the reaction mass isstirred at 25° C. for a period of eight hours.

The organic phase is separated from the aqueous phase and the aqueousphase is extracted with toluene. The toluene extract is combined withthe organic phase and the resulting product is distilled on a 2" splashcolumn yielding the following fractions:

    ______________________________________                                                Vapor    Liquid   Vacuum      Weight of                               Fraction                                                                              Temp.    Temp.    mm/Hg.      Fraction                                No.     (°C.)                                                                           (°C.)                                                                           Pressure    (Grams)                                 ______________________________________                                        1       37/85    76/100   /400        256                                     2        87      109       400        202                                     3        69      107      400-50      188                                     4       107      128      3.6         205                                     5       112      148                                                          6       120      175              2.0  9                                      7       120      180      1.0                                                                                       214                                     ______________________________________                                    

Fractions 4, 5 and 6 are bulked and redistilled on a 1"×10" Goodloecolumn yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight of                                  Fraction  Temp.   Temp.     mm/Hg. Fraction                                   No.       (°C.)                                                                          (°C.                                                                             Pressure                                                                             (Grams)                                    ______________________________________                                        1         72/93   108/115   2.17/2.11                                                                            13                                         2         93      116        2.01  17                                         3         93      117       2.0    19                                         4         94      118       2.0    27                                         5         95      117       2.0    25                                         6         93      118       2.1    10                                         7         95      118       2.1    20                                         8         95      120       2.1    15                                         9         95      126       2.1    17                                         10        90      200       2.1    15                                         ______________________________________                                    

FIG. 14 is the GLC profile for the crude reaction product prior todistillation (Conditions: Carbowax column programmed at 130°-220° C. at8° C. per minute).

FIG. 15 is the NMR spectrum of the compound having the structure:##STR297##

The compound having the structure: ##STR298## (bulked fractions 4-8) hasa camphoraceous aroma with early morning forest path, green, piney,woody and camphoraceous topnotes.

EXAMPLE VIII PREPARATION OF2-HYDROXY-4-METHYLENE-2,8-DIMETHYL-TRICYCLO[3.3.1.1³,7 ]DECAN (ALSONAMED 2,8-DIMETHYL-4-METHYLENE-2-ADAMANTOL) ##STR299##

In to a microvial reaction vessel placed in an ice bath and cooled to 0°C. is added 1 gram of lithium in 1 ml diethyl ether. To the resultingmixture is added 0.44 grams of the compound having the structure:##STR300## prepared according to Example VII. The reaction mixture ispermitted to stand for a period of 2.5 hours.

A mixture of 1:1 methanol:toluene is then added to the resultingproduct. 15 ml Saturated sodium chloride is then added to the resultingproduct. The resulting product is a solid.

FIG. 16 is a GLC profile of the reaction product. (Conditions: Carbowaxcolumn programmed at 130°-220° C. at 8° C. per minute). The peakindicated by reference numeral 162 is the peak for the compound havingthe structure: ##STR301##

The peak indicated by reference numeral 161 is for another isomer of thecompound having the structure: ##STR302##

The peak indicated by reference numeral 163 is for yet another isomer ofthe compound having the structure: ##STR303##

The peak indicated by reference numeral 164 is for the starting materialhaving the structure: ##STR304## a mixture of isomers having thestructures: ##STR305##

FIG. 17 is the NMR spectrum of the compound of peak 161 of FIG. 16; anisomer of the compound having the structure: ##STR306##

FIG. 18 is the NMR spectrum of the peak indicated by reference numeral162 of FIG. 16; an isomer of the compound having the structure:##STR307##

FIG. 19 is the NMR spectrum for the peak indicated by reference numeral163 of FIG. 16; another isomer of the compound having the structure:##STR308##

FIG. 20 is the NMR spectrum for the peak indicated by reference numeral164 of FIG. 16; for the compound having the structure: ##STR309## amixture of isomers having the structures: ##STR310##

EXAMPLE IX PREPARATION OF

4-METHYLENE-2,8-DIMETHYL-TRICYCLO[3.3.1.1.³,7 ]DECAN-2-YL ACETATE (ALSOHAVING the NAME 2,8-DIMETHYL-4-METHYLENE-2-ADAMANTOL ACETATE) ##STR311##

Into a 2 dram vial immersed in a 10 ml beaker equipped with water bathand hot plate is placed 0.71 grams of the compound having the structure:##STR312## and 0.34 grams of acetic anhydride. The resulting mixture isheated to 80°-100° C. for a period of one hour.

The resulting product has the structure: ##STR313##

FIG. 21 is the GLC profile of the crude reaction product containing thecompound having the structure: ##STR314##

EXAMPLE X PREPARATION OF 2-HYDROXY-4,8-DIMETHYL TRICYCLO[3.3.1.1³,7]DECAN (ALSO NAMED 2,8-DIMETHYL-2-ADAMANTOL) ##STR315##

Into a 1 liter Parr bomb is placed 543.9 grams of the compound havingthe structure: ##STR316## 200 ml isopropyl alcohol and 5.5 grams ofpalladium on carbon catalyst (10% palladium on carbon). The Parr bomb issealed and pressurized to 100 psig with hydrogen and maintained at atemperature of 100° C. with stirring for a period of two hours. At theend of the two hour period, the Parr bomb is cooled and the contents arefiltered.

The solvent (isopropyl alcohol) is stripped under vacuum and theresulting product is distilled on a 2" splash column yielding thefollowing fractions:

    ______________________________________                                                Vapor    Liquid   Vacuum      Weight of                               Fraction                                                                              Temp.    Temp.    mm/Hg.      Fraction                                No.     (°C.)                                                                           (°C.)                                                                           Pressure    (Grams)                                 ______________________________________                                        1        40/      99/                  16                                     2       119      141                  164                                     3       125      145      7                                                    4      125      150      7                                                                                         352                                     5       120      159      7                                                   ______________________________________                                    

Fractions 3 and 4 are bulked and redistilled on a 1"×10" Goodloe columnyielding the following fractions:

    ______________________________________                                               Vapor    Liquid   Vacuum        Weight of                              Fraction                                                                             Temp.    Temp.    mm/Hg. Reflux Fraction                               No.    (°C.)                                                                           (°C.)                                                                           Pressure                                                                             Ratio  Grams                                  ______________________________________                                        1      118/125  137/141  7.1/6.9                                                                              4:1    17                                     2      126      144      7.2    4:1    37                                     3      127      145      7.5    4:1    31                                     4      130      152      7.6    4:1    54                                     5      137      155      7.7    4:1    50                                     6      134      163      8.1    4:1    22                                     7      137      155      6.5    4:1    37                                     8      126      151      6.1    4:1    29                                     ______________________________________                                    

FIG. 22 is the GLC profile for the crude reaction product prior todistillation. The peak indicated by reference numeral 2200 is the peakfor the compound having the structure: ##STR317## The peak indicated byreference numeral 2200 is the peak for the compound having thestructure: ##STR318## (Conditions: Carbowax column programmed at130°-220° C. at 8° C. per minute).

FIG. 23 is the NMR spectrum for the compound having the structure:##STR319##

The compound having the structure: ##STR320## (bulked fractions 4 and 5)has a spicy, ginger root, rosemary and camphoraceous aroma profile withgreen, woody and ginger root topnotes.

EXAMPLE XI PREPARATION OF 4,8-DIMETHYL TRICYCLO[3.3.1.1³,7 ]DECAN-2-YLACETATE (ALSO NAMED 4,8-DIMETHYL-2-ADAMANTOL ACETATE ##STR321##

Into a 1 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle are placed 120 grams oftetrahydrofuran and 199 grams of the compound having the structure:##STR322## prepared according to Example X. The resulting mixture isheated to 110° C. Over a period of two hours, 130 grams of aceticanhydride is added to the reaction mass while maintaining thetemperature of the reaction mass at 110° C.

At the end of the addition period for the acetic anhydride, the reactionmass is cooled to 50°-60° C. and transferred to a distillation pot.

The resulting product is first stripped of excess acetic anhydride undervacuum and distilled on a 1"×10" Goodloe column yielding the followingfractions:

    ______________________________________                                                Vapor   Liquid   Vacuum        Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg. Reflux Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                             Ratio  (Grams)                                ______________________________________                                        1        54/    138/     20/    4:1    17                                     2        76     142      3.2    4:1    10                                     3       118     134      3.0    4:1    19                                     4       118     135      2.9    4:1    20                                     5       118     136      2.8    4:1    23                                     6       118     135      2.8    9:1    29                                     7       117     138      2.7    9:1    35                                     8       116     147      2.6    9:1    17                                     9       121     156      3.2    9:1    23                                     10      122     167      3.3    9:1    20                                     11      121     200      3.4    9:1    13                                     12      121     250             9:1     6                                     ______________________________________                                    

FIG. 24 is the GLC profile for the reaction product containing thecompound having the structure: ##STR323## (Conditions: Carbowax columnprogrammed at 130°-220° C. at 8° C. per minute).

FIG. 25 is the NMR spectrum for the compound having the structure:##STR324##

The compound having the structure: ##STR325## (bulked fractions 5-9) hasa woody, ambery, vetiver, cedarwood, piney and chrysanthemum-like aromaprofile with woody, amber and olibanum topnotes.

EXAMPLE XII CL PREPARATION OF 4,8-DIMETHYL-TRICYCLO[3.3.1.1³,7]DECAN-2-ONE (ALSO NAMED 4,8-DIMETHYL-2-ADAMANTANONE) ##STR326##

Into a 1 liter Parr bomb is placed 116 grams of methylethyl ketone; 2grams of a palladium on carbon catalyst (10% palladium on carbon) and115.5 grams (0.656 moles) of the compound having the structure:##STR327## The Parr bomb is closed and heated to 100° C. and pressurizedto a 100 psig-250 psig over a period of three hours with hydrogen. Atthe end of the three hour hydrogenation period, the Parr bomb is cooledand opened and the contents are filtered.

The filtrate is then distilled on a 2" splash column yielding thefollowing fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight of                                  Fraction  Temp.   Temp.     mm/Hg. Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (Grams)                                    ______________________________________                                        1         /96     /112      2.4    81.4                                       2         40      210       2.4    17.1                                       ______________________________________                                    

The distillation fractions are then redistilled on a 2 foot Goodloecolumn yielding the following fractions:

    ______________________________________                                                Vapor   Liquid   Vacuum        Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg. Reflux Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                             Ratio  (Grams)                                ______________________________________                                        1       82/89   119/127  1.6/1.6                                                                              9:1    14.1                                   2       89      128      1.6    9:1    9.1                                    3       95      146      3.0    9:1    8.1                                    4       98      205      3.0    9:1    13.3                                   5       98      230      1.6    9:1    3.6                                    ______________________________________                                    

FIG. 28 is the GLC profile for the crude reaction product prior todistillation (Conditions: SE-30 column programmed at 130°-220° C. at 8°C. per minute).

The resulting product has the structure: ##STR328## as confirmed by NMR,IR and mass spectral analyses.

EXAMPLE XIII PREPARATION OF 4,8-DIMETHYL-TRICYCLO[3.3.1.1³,7 ]DECAN-2-YLACETATE (ALSO NAMED 4,8-DIMETHYL-2-ADAMANTOL ACETATE) ##STR329##

Into a 2 liter Parr bomb is placed 6 grams of 10% palladium on carboncatalyst; 600 grams of the compound having the structure: ##STR330## TheParr bomb is sealed and pressurized to 100 psig with hydrogen and heatedat 100° C. for a period of 1.2 hours. At the end of the 1.2 hour period,the Parr bomb is cooled and the contents are filtered and distilled at116°-118° C.; 2.6-3.0 mm/Hg. yielding 20 fractions.

FIG. 29 is the GKLC profile of the reaction prior to distillationcontaining the compound having the structure: ##STR331##

This compound has a woody, amber, vetiver, cedarwood, pine,chrysanthemum-like aroma with woody, olibanum and amber topnotes.(Bulked distillation fractions 2-18).

EXAMPLE XIV "OXO" REACTION PRODUCT PRODUCED BY REACTION OF CARBONMONOXIDE AND HYDROGEN ON 2-HYDROXY-4-METHYLENE-8-METHYLTRICYCLO[3.3.1.1³,7 ]DECAN ##STR332## PART I PRODUCTION OF OXO REACTIONCATALYST

150 ml Methanol is admixed with 18 grams of triphenyl phosphine, 0.6grams of RhCl₃.H₂ O and 1.2 grams of sodium bicarbonate. The resultingmixture is heated at reflux for a period of one hour and then cooled.

PART II OXO REACTION

Into a 2 liter autoclave rated for 1000 psig pressure and containingheating elements is placed 409.6 grams of the compound having thestructure: ##STR333## and 742 grams of toluene together with the oxoreaction catalyst prepared in Part I. The autoclave is sealed and heatedto 100° C. and pressurized to 600 psig using a 50:50 mole:mole mixtureof carbon monoxide and hydrogen. The autoclave pressure is thenmaintained at 600 psig and 100° C. for a period of 6.5 hours. At the endof the 6.5 hour period, the autoclave is depressurized, the contents arecooled and the autoclave is opened. The contents of the autoclave arethen distilled using a 2" splash column yielding the followingfractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight of                                  Fraction  Temp.   Temp.     mm/Hg. Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (Grams)                                    ______________________________________                                        1         /37     /63       /100   75.5                                       2          43     105       100    78.8                                       3          30     110       80     21.5                                       4          85     154       70     53.3                                       5         128     175       80     107.0                                      6         155     186       80     105.8                                      7         159     194       2.3    98.1                                       8         120     220       1.4    53.9                                       ______________________________________                                    

FIG. 30 is the GLC profile for the crude reaction product prior todistillation (Conditions: SE-30 column programmed at 130°-220° C. at 8°C. per minute).

The peak indicated by reference numeral 301 is the peak for methylalcohol solvent. The peak indicated by reference numeral 302 is the peakfor the toluene solvent. The peak indicated by reference numeral 303 isthe peak for the compound having the structure: ##STR334##

The peak indicated by reference numeral 304 is the peak for the compoundhaving the structure: ##STR335##

The peak indicated by reference numeral 305 is the peak for the compoundhaving the structure: ##STR336##

FIG. 31 is the GLC profile for distillation fraction 6 of the foregoingdistillation (Conditions: SE-30 column programmed at 130°-220° C. at 8°C. per minute).

FIG. 32 is the GLC profile for distillation fraction 7 of the foregoingdistillation (Conditions: SE-30 column programmed at 130°-220° C. at 8°C. per minute).

FIG. 33 is the NMR spectrum for the peak indicated by reference numeral303 on FIG. 30 for the compound having the structure: ##STR337##

FIG. 34 is the NMR spectrum for the peak indicated by reference numeral304 on FIG. 30; for the compound having the structure: ##STR338##

FIG. 35 is the NMR spectrum for the peak indicated by reference numeral305 on FIG. 30; for the compound having the structure: ##STR339##

FIG. 36 is the NMR spectrum for distillation fraction 6 of the foregoingdistillation showing the existence of the three compounds having thestructures: ##STR340##

FIG. 37 is the NMR spectrum for distillation fraction 7 of the foregoingdistillation.

The mixture of compounds having the structures: ##STR341## has a green,woody and fir balsum pine-like aroma profile.

EXAMPLE XV PREPARATION OF ETHERIFIED REACTION PRODUCT OF2-HYDROXY-4-METHYLENE-8-METHYL TRICYCLO[3.3.1.1³,7 ]DECAN ##STR342##with production of byproducts having the structures: ##STR343##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle are placed 120 grams of tertiarybutyl methyl ether; 500 grams of the compound having the structure:##STR344## and 115 grams of Amberlyst® 15 (a styrene sulfonic acid ionexchange catalyst manufactured by the Rome & Haas Company ofPhiladelphia, Pa.). The resulting mixture is heated to 35°-40° C. Overan eight hour period, 1168 grams of isobutylene is added to the reactionmass. At the end of the addition of the isobutylene the reaction mass iscooled and washed with 10% sodium bicarbonate.

The resulting product was fractonally distilled on a stone-packed columnyielding the following fractions:

    ______________________________________                                                Vapor    Liquid   Vacuum      Weight of                               Fraction                                                                              Temp.    Temp.    mm/Hg.      Fraction                                No      (°C.)                                                                           (°C.)                                                                           Pressure    (Grams)                                 ______________________________________                                        1       42/59    73/118   220                                                 2        54      142       90         38                                      3       80/92    116/124  2.0/1.6     50                                      4       101      128      1.6         91                                      5       110      143      1.6         87                                      6       138      178      1.3         65                                       7      142      208      1.2                                                                                       17                                      8       140      214      1.1                                                 ______________________________________                                    

FIG. 37A is the GLC profile for the reaction product prior todistillation. The peak group indicated by reference numeral 370 is forthe compound having the structure: ##STR345## (Conditions: Carbowaxcolumn programmed at 130°-220° C. at 8° C. per minute).

FIG. 37B is the GLC profile for distillation fraction 3 of the foregoingdistillation. The peak group indicated by reference numeral 371 is forthe compound having the structure: ##STR346##

FIG. 38 is the NMR spectrum for peak group 371 of FIG. 37B fordistillation fraction 3 of the foregoing distillation; for the compoundhaving the structure: ##STR347##

FIG. 37C is the GLC profile for distillation fraction 3 of the foregoingdistillation. The peak indicated by reference numeral 372 is the peakfor the newly formed isomers of the starting material having thestructure: ##STR348##

FIG. 39 is the GLC profile for distillation fraction 6 of the foregoingdistillation. The peak indicated by reference numeral 391 is the peakfor the compound having the structure: ##STR349## The peak indicated byreference numeral 392 is the peak for one or both of the compoundshaving the structures: ##STR350## The peak indicated by referencenumeral 393 is the peak for the compound having the structure:##STR351## The peak indicated by reference numeral 394 is the peak forthe starting materials having the structures: ##STR352## The peakindicated by reference numeral 395 is the peak for one or both of thecompounds having the structures: ##STR353##

FIG. 40 is the NMR spectrum for the peak indicated by reference numeral392 of the GLC profile of FIG. 39 for one or both of the compoundshaving the structures: ##STR354##

FIG. 41 is the NMR spectrum for the peak indicated by reference numeral393 of the GLC profile of FIG. 39 for the compound having the structure:##STR355##

FIG. 42 is the NMR spectrum for the peak indicated by reference numeral394 of the GLC profile of FIG. 39 for the compounds having thestructures: ##STR356##

FIG. 43 is the NMR spectrum for the peak indicated by reference numeral395 of the GLC profile of FIG. 39 for one or both of the compoundshaving the structures: ##STR357##

FIG. 44 is the NMR spectrum for the peak indicated by reference numeral372 of FIG. 37C for the newly formed isomers of the starting materialhaving the structures: ##STR358##

Fraction 6 has an intense and long-lasting camphoraceous aroma withsweet, camphoraceous topnotes.

EXAMPLE XVI PREPARATION OF2-HYDROXY-4,8-DIMETHYL-4-METHOXY-TRICYCLO[3.3.1.1³,7 ]DECAN

Reactions: ##STR359## (wherein M₁ is sodium) and ##STR360## (wherein M₁is sodium).

Into a 250 ml reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle are placed 40 ml toluene, 50 grams of thecompound having the structure: ##STR361## and 1.5 grams of ALIQUAT® 336(Tricapryl methyl ammonium chloride phase transfer agent produced byHenkel Chemicals Inc. at Minneapo, Minn.). The resulting productexotherms 229° C. 49 Grams of 50% aqueous sodium hydroxide is added tothe reaction mass. The reaction mass is then heated to 45° C. and 38grams of dimethyl sulfate is added to the reaction mass with stirringover a period of 0.5 hours during which time the reaction masstemperature goes up to 51° C. The reaction mass is then stirred at45°-52° C. for a period of eight hours. At the end of the eight hourperiod, GLC analysis indicates no further conversion.

FIG. 45 is the GLC profile for the crude reaction product. The peakindicated by reference numeral 450 is the peak for the compound havingthe structure: ##STR362##

The peak indicated by reference numeral 451 is the peak for the startingmaterial having the structure: ##STR363##

FIG. 46 is the NMR spectrum for the peak indicated by reference numeral450 of FIG. 45; for the compound having the structure: ##STR364##

EXAMPLE XVII PERFUME FORMULATION

The following "woody cologne" perfume formulations are prepared:

    ______________________________________                                                       XVII  XVII    XVII    XVII                                                    (A)   (B)     (C)     (D)                                      ______________________________________                                        Bergamot Oil     150     150     150   150                                    Orange oil       200     200     200   200                                    Lemon oil        50      50      50    50                                     Eugenol          10      10      10    10                                     4-(4-Methyl-4-hydroxy amyl)                                                                    40      40      40    40                                     Δ.sup.3 cyclohexene                                                     carboxaldehyde                                                                Ylang oil        2       2       2     2                                      Petigrain Paraguay                                                                             10      10      10    10                                     Gamma methyl ionone                                                                            20      20      20    20                                     Vetiver Venezuela                                                                              18      18      18    18                                     3-Alpha-Methyl dodecahydro-                                                                    5       5       5     5                                      6,6,9a-trimethylnaptho-                                                       [2,1-b]furan                                                                  Product produced by                                                                            5       5       5     5                                      reaction of acetic                                                            anhydride polyphosphoric                                                      acid and 1,5,9-tri-                                                           methyl cyclododecatriene-                                                     1,5,9 according to the                                                        process of Example I of                                                       U.S. Letters Pat.                                                             No. 3,718,698 the                                                             specification for which                                                       is incorporated by                                                            reference herein                                                              Octahydro-9,9-dimethyl-                                                                        50      50      50    50                                     1,6-methanonaphthalene-                                                       1-(2H)-ol produced                                                            according to Example III                                                      of U.S. Letters Pat.                                                          No. 3,996,169 the                                                             specification for which                                                       is incorporated by                                                            reference herein.                                                             The compound having                                                                            12      0       0     0                                      the structure:                                                                 ##STR365##                                                                   produced according                                                            to Example III,                                                               bulked fractions 6-9.                                                         The compound having                                                                            0       12      0     0                                      the structure:                                                                 ##STR366##                                                                   produced according                                                            to Example III(A).                                                            The compound having                                                                            0       0       12    0                                      the structure:                                                                 ##STR367##                                                                   produced according                                                            to Example IV,                                                                bulked fractions                                                              8-18.                                                                         The compound having                                                                            0       0       0     12                                     the structure:                                                                 ##STR368##                                                                   produced according                                                            to Example V(B),                                                              bulked fractions                                                              7-9.                                                                          ______________________________________                                    

The compound having the structure ##STR369## produced according toExample III, imparts to this woody cologne formulation a sandalwood,woody, patchouli, rhubarb, ginger, minty and amyris undertone withamyris, camphoraceous, patchouli, woody and piney topnotes. Accordigly,the perfume formulation of Example XVII(A) can be described as "woodycologne with sandalwood, woody, patchouli, rhubarb, ginger, minty andamyris undertones and amyris, camphoraceous, patchouli, woody and pineytopnotes".

The compound having the structure: ##STR370## prepared according toExample III(A), imparts to this woody cologne formulation acamphoraceous, ginger, cardamon and woody undertones. Accordingly, theperfume formulatuion of Example XVII(B) can be described as "woodycologne with camphoraceous, gingery, cardamon and woody undertones".

The compound having the structure: ##STR371## imparts to this woodycologne formulation a woody, cedarwood-like, sandalwood-like,camphoraceous, minty and earthy undertones, with cedarwood, sandalwood,patchouli, camphoraceous, herbaceous, incense and olibanum topnotes.Accordingly, the perfume formulation of Example XVII(C) can be describedas "woody cologne with woody, cedarwood-like, sandalwood-like,camphoraceous, minty and earthy undertones and cedarwood, sandalwood,patchouli, camphoraceous, herbaceous, incense and olibanum topnotes".

The compound having the structure: ##STR372## produced according toExample V(B), bulked fractions 7-9, imparts to this woody cologneformulation cedarwood-like, patchouli, vetiver, peppery, grapefruitpeel-like and camphoraceous undertones with woody, vetiver, grapefruitpeel-like topnotes. Accordingly, the perfume formulation of ExampleXVII(D) can be described as "woody cologne with cedarwood-like,patchouli, vetiver, peppery, grapefruit peel-like and camphoraceousundertones and woody, vetiver and grapefruit peel-like topnotes".

EXAMPLE XVIII PINE FRAGRANCE

The following pine fragrance formulations are prepared:

    ______________________________________                                                       XVIII XVIII   XVIII   XVIII                                                   (A)   (B)     (C)     (D)                                      ______________________________________                                        Isobornyl acetate                                                                              100     100     100   100                                    Camphor          10      10      10    10                                     Alpha-Terpineol  25      25      25    25                                     Fir balsam absolute                                                                            20      20      20    20                                     (50% in diethyl                                                               phthalate)                                                                    Coumarin         4       4       4     4                                      Linalool         30      30      30    30                                     Fenchyl alcohol  10      10      10    10                                     Anethol          12      12      12    12                                     Lemon terpenes washed                                                                          50      50      50    50                                     Borneol          5       5       5     5                                      Galbanum oil     5       5       5     5                                      Turpentine Russian                                                                             150     150     150   150                                    Eucalyptol       50      50      50    50                                     2,2,6-trimethyl-1-                                                                             12      12      12    12                                     cyclo-hexene-1-                                                               carboxaldehyde                                                                Maltol (1% in diethyl                                                                          5       5       5     5                                      phthalate                                                                     The compound having                                                                            28      0       0     0                                      the structure:                                                                 ##STR373##                                                                   produced according                                                            Example VI, bulked                                                            fractions 10-16.                                                              The compound having                                                                            0       28      0     0                                      the structure:                                                                 ##STR374##                                                                   produced according                                                            to Example VI, bulked                                                         fractions 5-19.                                                               The compound having                                                                            0       0       28    0                                      the structure:                                                                 ##STR375##                                                                   produced according                                                            to Example VII, bulked                                                        fractions 4-8.                                                                The compound having                                                                            0       0       0     28                                     the structure:                                                                 ##STR376##                                                                   produced according                                                            to Example X,                                                                 bulked fractions                                                              4 and 5.                                                                      ______________________________________                                    

The compound having the structure: ##STR377## prepared according toExample VI, bulked fractions 10-16 imparts to this pine formulation awoody, rose-like and peony-like undertone, with floral, sweet pea, roseand peony topnotes. Accordingly, the perfume formulation of ExampleXVIII(A) can be described as "piney, with woody, rose-like andpeony-like undertones and floral sweet pea, rose and peony topnotes".

The compound having the structure: ##STR378## prepared according toExample VI, bulked fractions 5-19 imparts to this pine formulation anambery, woody, cedarwood-like undertone with fruity and woody topnotes.Accordingly, the perfume formulations of Example XVIII(B) can bedescribed as "piney with ambery, woody and cedarwood-like undertones andfruity and woody topnotes".

The compound having the structure: ##STR379## prepared according toExample VII bulked fractions 4-8 imparts to this piney formulationcamphoraceous undertones with early morning forest path, green, piney,woody and camphoraceous topnotes. Accordingly, the perfume formulationof Example XVIII(C) can be described as "piney with camphoraceousundertones and early morning forest path, green, piney, woody andcamphoraceous topnotes".

The compound having the structure: ##STR380## produced according toExample X bulked fractions 4 and 5 imparts to this piney formulationspicy, ginger root, rosemary and camphoraceous undertones with green,woody and ginger root topnotes. Accordingly, the perfume formulation ofExample XVIII(D) can be described as "piney with spicy, ginger root,rosemary and camphoraceous undertones and green, woody and ginger roottopnotes".

EXAMPLE XIX FLORAL PERFUME COMPOSITIONS

The following floral fragrance formulations are prepared:

    ______________________________________                                                       FLORAL FRAGRANCE                                                              XIX   XIX     XIX     XIX                                                     (A)   (B)     (C)     (D)                                      ______________________________________                                        Citronellol      12.3    12.3    12.3  5.0                                    Geraniol         2.5     2.5     2.5   5.0                                    Amyl Cinnamic Aldehyde                                                                         24.6    24.6    24.6  5.0                                    Galaxolide ® 50                                                                            9.8     9.8     9.8   5.0                                    (Trademark for Tricyclic                                                      Isochroman of                                                                 International Flavors &                                                       Fragrances Inc.)                                                              Vertenex High Cis                                                                              7.4     7.4     7.4   5.0                                    (Cis-t-Butylcyclo                                                             hexenyl Acetate;                                                              Para Isomer)                                                                  Rose Oxide       0.7     0.7     0.7   5.0                                    Cinnamic Alcohol 19.6    19.6    19.6  5.0                                    Aldehyde C-11    0.5     0.5     0.5   5.0                                    (n-Undecylenic                                                                Aldehyde)                                                                     Aldehyde C-12    0.5     0.5     0.5   5.0                                    (n-Dodecyl Aldehyde                                                           in 10% solution in                                                            diethyl phthalate)                                                            Citronellal (10% 0.5     0.5     0.5   5.0                                    solution in diethyl                                                           phthalate)                                                                    Phenyl Ethyl Acetate                                                                           2.5     2.5     2.5   5.0                                    Ylang Oil        1.2     1.2     1.2   5.0                                    Indisan (Hydrogenated                                                                          3.7     3.7     3.7   5.0                                    derivative of reaction                                                        product of Camphene and                                                       Resorcinol)                                                                   Musk Ketone      5.0     5.0     5.0   5.0                                    Oakmoss Resin    0.5     0.5     0.5   0.5                                    Liatrix Absolute 2.5     2.5     2.5   5.0                                    (10% in diethyl                                                               phthalate)                                                                    Vetiver Acetate  1.2     1.2     1.2   5.0                                    Diethyl Phthalate                                                                              5.0     5.0     5.0   5.0                                    The mixture of compounds                                                                       0.0     0.0     15.0  0.0                                    having the structures:                                                         ##STR381##                                                                    ##STR382##                                                                    ##STR383##                                                                   and                                                                            ##STR384##                                                                   produced according                                                            to Example XIV,                                                               fraction 6.                                                                   Mixture of compounds                                                                           0.0     0.0     0.0   35.0                                   having the structures:                                                         ##STR385##                                                                    ##STR386##                                                                    ##STR387##                                                                    ##STR388##                                                                    ##STR389##                                                                    ##STR390##                                                                    ##STR391##                                                                   and                                                                            ##STR392##                                                                   prepared according                                                            to Example XV.                                                                ______________________________________                                    

The compound havinng the structure: ##STR393## produced according toExample XI, bulked fractions 5-9 imparts to this floral fragranceformulation woody, ambery, vetiver, cedarwood, piney andchrysanthemum-like undertones with woody, amber and olibanum topnotes.Accordngly, the fragrance formulation of Example XIX(A) can be describedas "floral with woody, amber, vetiver, cedarwood, piney andchrysanthemum-like unertones and woody, amber and olibanum topnotes".

The compound having the structure: ##STR394## prepared according toExample XIII, bulked fractions 2-18 imparts to this floral fragrance awoody, amber, vetiver, cedarwood, piney and chrysanthemum-likeundertone, with woody, amber and olibanum topnotes. Accordingly, thefragrance formulation of Example XIX(B) can be described as "floral withwoody, amber, vetiver, cedarwood, piney and chrysanthemum-likeundertones and woody, amber, olibanum topnotes".

The mixture of compounds having the structures: ##STR395## preparedaccording to Example XIV, fraction 6 imparts to this floral formulationa green, woody and fir balsam-like undertones. Accordingly, thefragrance formulation of Example XIX(C) can be described as "floral withgreen, woody and fir balsam-like undertones".

The mixture of compounds having the structures: ##STR396## producedaccording to Example XV, imparts to this floral fragrance acamphoraceous undertone with sweet camphoraceous topnotes. Accordingly,the fragrance formulation of Example XIX(D) can be described as "floralwith a camphoraceous undertone and sweet camphoraceous topnotes".

EXAMPLE XX PREPARATION OF COSMETIC POWDER COMPOSITIONS

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table II below:

                  TABLE II                                                        ______________________________________                                        SUBSTANCE      AROMA Description                                              ______________________________________                                        The compound having                                                                          A sandalwood, woody,                                           the structure: patchouli, rhubarb, ginger,                                     ##STR397##    minty and amyris aroma profile with amyris, camphoraceous,                    patchouli, woody and piney topnotes.                           produced according                                                            to Example III, bulked                                                        fractions 6-9.                                                                The compound having                                                                          A camphoraceous, gingery,                                      the structure: cardamon and woody profile.                                     ##STR398##                                                                   produced according                                                            to Example III(A).                                                            The compound having                                                                          A woody, cedarwood-like,                                       the structure: sandalwood-like,                                                ##STR399##    camphoraceous, minty and earthy aroma profile with                            cedarwood, sandalwood, patchouli, camphoraceous, herbaceous                   , incense and olibanum topnotes.                               produced according                                                            to Example IV, bulked                                                         fractions 8-18.                                                               The compound having                                                                          A cedarwood-like, patchouli,                                   the structure: vetiver, peppery, grapefruit                                    ##STR400##    peel-like and camphoraceous aroma profile, with woody,                        vetiver and grapefruit peel topnotes.                          prepared according                                                            to Example V(B), bulked                                                       fractions 7-9.                                                                The compound having                                                                          A woody, rose-like and peony-                                  the structure: like aroma profile, with                                        ##STR401##    floral, sweet pea, rose and peony topnotes.                    produced according                                                            to Example VI, bulked                                                         fractions 10-16.                                                              The compound having                                                                          An ambery woody and cedar-                                     the structure: wood-like aroma profile,                                        ##STR402##    with fruity and woody topnotes.                                produced according                                                            to Example VI, bulked                                                         fractions 5-19.                                                               The compound having                                                                          A camphoraceous aroma with                                     the structure: early morning forest path,                                      ##STR403##    green, piney, woody and camphoraceous topnotes.                produced according                                                            to Example VII, bulked                                                        fractions 4-8.                                                                The compound having                                                                          A spicy, ginger root,                                          the structure: rosemary and camphoraceous                                      ##STR404##    aroma profile, with green, woody and ginger                                   root topnotes.                                                 produced according                                                            to Example X, bulked                                                          fractions 4 and 5.                                                            The compound having                                                                          A woody, ambery, vetiver,                                      the structure: cedarwood, piney and                                            ##STR405##    chrysanthemum-like aroma profile, with woody, amber and                       olibanum topnotes.                                             produced according                                                            to Example XI, bulked                                                         fractions 5-9.                                                                The compound having                                                                          A woody, amber, vetiver,                                       the structure: cedarwood, piney and                                            ##STR406##    chrysanthemum-like aroma profile, with woody, amber and                       olibanum topnotes.                                             produced according                                                            to Example XIII, bulked                                                       fractions 2-18.                                                               Mixture of compounds                                                                         A green, woody and fir                                         having the structures:                                                                       balsam-like aroma profile.                                      ##STR407##                                                                    ##STR408##                                                                    ##STR409##                                                                   and                                                                            ##STR410##                                                                   produced according                                                            to Example XIV,                                                               distillation fraction 6.                                                      Mixture of compounds                                                                         A comphoraceous aroma with                                     having the structures:                                                                       sweet, camphoraceous topnotes.                                  ##STR411##                                                                    ##STR412##                                                                    ##STR413##                                                                    ##STR414##                                                                    ##STR415##                                                                    ##STR416##                                                                    ##STR417##                                                                   and                                                                            ##STR418##                                                                   produced according                                                            to Example XV.                                                                Fragrance formulation                                                                        Woody cologne with sandalwood,                                 of Example XVII(A).                                                                          woody, patchouli, rhubarb,                                                    ginger, minty and amyris                                                      undertones and amyris,                                                        camphoraceous, patchouli,                                                     woody and piney topnotes.                                      Fragrance formulation                                                                        Woody cologne with                                             of Example XVII(B).                                                                          camphoraceous, gingery,                                                       cardamon and woody undertones.                                 Fragrance formulation                                                                        Woody cologne with woody,                                      of Example XVII(C).                                                                          cedarwood-like,                                                               sandalwood-like,                                                              camphoraceous, minty and                                                      earthy undertones and                                                         cedarwood, sandalwood,                                                        patchouli, camphoraceous,                                                     herbaceous, incense and                                                       olibanum topnotes.                                             Fragrance formulation                                                                        Woody cologne with cedarwood-                                  of Example XVII(D).                                                                          like, patchouli, vetiver,                                                     peppery, grapefruit                                                           peel-like, and camphoraceous                                                  undertones and woody, vetiver                                                 and grapefruit peel-like                                                      topnotes.                                                      Fragrance formulation                                                                        Piney, with woody, rose-like                                   of Example XVIII(A).                                                                         and peony-like undertones and                                                 floral sweet peak, rose and                                                   peony topnotes.                                                Fragrance formulation                                                                        Piney with ambery, woody and                                   of Example XVIII(B).                                                                         cedarwood-like undertones and                                                 fruit and woody topnotes.                                      Fragrance formulation                                                                        Piney with camphoraceous                                       of Example XVIII(C).                                                                         undertones and early morning                                                  forest path, green, piney,                                                    woody and camphoraceous                                                       topnotes.                                                      Fragrance formulation                                                                        Piney with spicy, ginger root,                                 of Example XVIII(D).                                                                         rosemary and comphoraceous                                                    undertones and green, woody                                                   and ginger root topnotes.                                      Fragrance formulation                                                                        Floral with woody, amber,                                      of Example XIX(A).                                                                           vetiver, cedarwood, piney and                                                 chrysanthemum-like undertones                                                 and woody, amber and olibanum                                                 topnotes.                                                      Fragrance formulation                                                                        Floral with woody, amber,                                      of Example XIX(B).                                                                           vetiver, cedarwood, piney and                                                 chrysanthemum-like undertones                                                 and woody, amber, olibanum                                                    topnotes.                                                      Fragrance formulation                                                                        Floral with green, woody and                                   of Example XIX(C).                                                                           fir balsam-like undertones.                                    Fragrance formulation                                                                        Floral with a camphoraceous                                    of Example XIX(D).                                                                           undertone and sweet                                                           camphoraceous topnotes.                                        The compound having                                                                          A fresh, camphoraceous, sage-                                  the structure: like and woody aroma profile,                                   ##STR419##     with camphoraceous and woody topnotes.                        prepared according                                                            to Example XII,                                                               bulked fractions 4-6.                                                         The compound having                                                                          A natural, fresh pine,                                         the structure: forest aroma profile.                                           ##STR420##                                                                   produced according                                                            to Example XVI.                                                               ______________________________________                                    

EXAMPLE XXI PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with aromas as set forth in Table II ofExample XX (which detergents are prepared from Lysine salt of n-dodecylbenzene sulfonic aicd as more specifically described in the U.S. Pat.No. 3,948,818 issued on Apr. 6, 1976, the specification for which isincorporated by refereince herein) are prepared containing each of thesubstances set forth in Table II of Example XX, supra. They are preparedby adding and homogeneously mixing the appropriate quantity of perfumerysubstance as set forth in Table II of Example XX in the liquiddetergent. The detergents all possess aromas as set forth in Table II ofExample XX, the intensity increasing with greater concentrations ofperfumery substance of Table II of Example XX, supra.

EXAMPLE XXII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The perfume substances of Table II of Example XX, supra, areincorporated into colognes at concentrations of 1.5%, 2.0%, 2.5%, 3.0%and 4.0% in 80%, 85% and 90% aqueous ethanol; and into a handkerchiefperfume composition at concentrations of 10%, 15%, 20%, 25% and 30% (in85%, 90% and 95% aqueous ethanol). Distinct and definitive aromas as setforth in Table II of Example XX are imparted to the cologne and to thehandkerchief perfume compositions.

EXAMPLE XXIII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (a non-ionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Letter Patent No. 985,190 issued on Mar. 9, 1976, thedisclosure of which is incorporated by reference herein) is mixed with0.15 grams of each of the substances homogeneous compositions areobtained. These compositions have excellent aromas as set forth in TableII of Example XX.

EXAMPLE XXIV PREPARATION OF SOAP

Each of the perfumery substances of Table II of Example XX areincorporated into soap (LVU-1) at 0.1% by weight of each substance.After two weeks in the oven at 90° F., each of the soaps showed novisual effect from the heat. Each of the soaps manifested an excellentaroma as set forth in Table II of Example XX, supra.

EXAMPLE XXV PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips (IVORY®, registered trademark of theProcter & Gamble Co. of Cincinnati, Ohio) are mixed individually withone gram each of the perfumery substances of Table II of Example XX,supra, until a homogeneous composition is obtained. The homogeneouscomposition is then treated under three atmospheres pressure at 180° C.for a period of three hours and the resulting liquid is placed into asoap mold. the resulting soap cakes, on cooling, manifest excellentaromas as set forth in Table II of Example XX, supra.

EXAMPLE XVI PREPARATION OF A SOLID DETERGENT COMPOSITION

A detergent is prepared from the following ingredients according toExample I of Canadian Letters Patent No. 1,007,948, the specificationfor which is incorporated by reference herein.

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        "Neodol 45-11" (a C.sub.14 -C.sub.15                                                               12                                                       alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate     55                                                       Sodium citrate       20                                                       Sodium sulfate, water brighteners                                                                  q.s.                                                     ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent is admixed separately with 0.15 grams of each of theperfume substances of Table II of Example XX, supra. The detergentsamples each have excellent aromas as set forth in Table II of ExampleXX, supra.

EXAMPLE XXVII

Utilizing the procedure os Example I at column 15 of U.S. Pat. No.3,632,396 (the specification for which is incorporated by referenceherein), a non-woven cloth substrate useful as a dryer-added fabricsoftening article of manufacture is prepared, wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.);

57% C₂₀₋₂₂ HAPS;

22% isopropyl alcohol;

20% antistatic agent;

1% of one of the perfume substances of Table II of Example XX, supra.

A fabric softening composition prepared as set forth above having theabove aroma characteristics as set forth in Table II of Example XX,supra, essentially consists of a substrate having a weight of about 3grams per 100 square inches, a substrate coating of about 1.85 grams per100 square inches of substrate and an outer coating of about 1.4 gramsper 100 square inches of substrate, thereby providing a total aromatizedsubstrate and outer coating weight ratio of about 1:1 by weight ofsubstrate. The aroma set forth in Table II of Example XX is imparted ina pleasant manner to the headspace in the dryer on operation thereof,using said dryer-added fabric softening non-woven fabric.

EXAMPLE XXVIII TOBACCO FLAVOR FORMULATION

Cigarettes are produced using the following tobacco formulation:

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        Bright           40.1                                                         Burley           24.9                                                         Maryland         1.1                                                          Turkish          11.6                                                         Stem (flue-cured)                                                                              14.2                                                         Glycerine        2.8                                                          H.sub.2 O        5.3                                                          ______________________________________                                        Ethyl butyrate   .05                                                          Ethyl valerate   .05                                                          Maltol           2.00                                                         Cocoa Extract    26.00                                                        Coffee Extract   10.00                                                        Ethyl Alcohol (95%)                                                                            20.00                                                        H.sub.2 O        41.90                                                        ______________________________________                                    

To 50% of the cigarettes, 10 and 20 ppm of one of the compounds setforth in Table III are added. These cigarettes are hereinafter called"experimental" cigarettes and the cigarettes without the adamantanederivatives in the following table are hereinafter called "control"cigarettes. The control and experimental cigarettes are then evaluatedby paired comparison and the results are as set forth in Table IIIbelow.

All cigarettes both control and experimental are evaluated for smokeflavor with 20 mm cellulose acetate filters.

                  TABLE III                                                       ______________________________________                                        Adamantane       Smoking Tobacco                                              Derivative       Flavor Evaluation                                            ______________________________________                                        The compound having                                                                            An intense, oriental                                         the structure:   Turkish-like flavor with                                      ##STR421##      patchouli and gingery nuances both prior to and on                            smoking.                                                     produced according                                                            to Example III, bulked                                                        fractions 6-9.                                                                The compound having                                                                            An oriental/incense aroma                                    the structure:   and taste prior to and on                                     ##STR422##      smoking causing the Virginia tobacco to have "Turkish                         tobacco" nuances on smoking.                                 produced according                                                            to Example IV, bulked                                                         fractions 8-18.                                                               The compound having                                                                            An oriental aroma and taste                                  the structure:   prior to and on smoking in                                    ##STR423##      the main stream and in the side stream causing the                            Virginia-like tobaccos to be more "Turkish-like". Also                        present are pleasant vetiver-like nuances.                   prepared according                                                            to Example V(B), bulked                                                       fractions 7-9.                                                                ______________________________________                                    

EXAMPLE XXIX

A fabric washing deodorant detergent powder product is prepared byadmixing the following ingredients:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Linear alkylbenzene sulfonate                                                                      9.0                                                      C.sub.13 -C.sub.15 straight chain                                                                  4.0                                                      alcolohols (30:30:40 mixture                                                  of C.sub.13, C.sub.14 and C.sub.15                                            straight chain alcohol)                                                       Sodium tripolyphosphate                                                                            16.0                                                     ZEAOLIGHT            8.0                                                      Sodium silicate      4.0                                                      Magnesium silicate   0.8                                                      Ethylene diamine     0.6                                                      N,N,N',N'[tetra(methylene                                                                          0.9                                                      phosphonic acid)] sodium                                                      carboxy methyl cellulose                                                      Anti-foam            1.5                                                      Sodium Perborate tetrahydrate                                                                      14.0                                                     N,N,N',N'-Tetraacetyl                                                                              4.2                                                      Glycoluril                                                                    The compound having  4.45                                                     the structure:                                                                 ##STR424##                                                                   prepared according                                                            to Example XVI.                                                               Water                45.0                                                     Sodium sulfate       5.0                                                      ______________________________________                                    

The resulting fabric washing deodorant detergent powder on use givesrise to a very pleasant "fresh pine forest" aroma without anyaesthetically displeasing aromas susequent to washing of fabrics in thestandard washing machine cycle.

Deodorant detergent products have also been prepared according toExamples I-IX of U.S. Letters Patent No. 4,304,679 incorporated byreference herein.

Thus, exemplified herein by reference are the following:

(a) a deodorant detergent product comprising:

(i) from 0.5 to 99.99% by weight of a non-soap detergent activecompound; and

(ii) from 0.01 to 10% by weight of a deodorant composition comprisingfrom 45 to 100% by weight of at least one adamantane derivative of ourinvention having the structure: ##STR425## (prepared according toExample XVI) or the adamantane derivative of our invention having thestructure: ##STR426## produced according to Example X, supra, bulkedfractions 4 and 5; said adamantane derivative having alipoxidase-inhibiting capacity of at least 50% or a Raoult varianceratio of at least 1.1 as stated in said U.S. Letters Patent No.4,304,679, wit the adamantane derivatives having the structures:##STR427## having deodorant values of from 0.5 to 3.5 as measured by thedeodorant value test as specifically set forth in said U.S. LettersPatent No. 4,304,679 and exemplified therein.

Furthermore, the examples of U.S. Letters Patent No. 4,663,068 are alsoincorporated herein by reference.

(i) from 5 to 40% by weight of a non-soap detergent active compoundcomprising an anionic detergent active compound;

(ii) from 1 to 90% of a non-soap detergency builder;

(iii) from 1 to 30% by weight a peroxy bleach compound together with anactivator therefor;

(iv) from 0.1 up to 10% by weight of a bleach stable perfume whichcomprises 50-100% by weight of at least one bleach stable adamantanederivative having the structures: ##STR428## having aLipoxidase-inhibiting capacity of at least 50% or a Raoult varianceratio of at least 1.1 as defined accordig to U.S. Letters Patent No.4,663,068 incorporated by reference herein, with the adamantanederivatives being stable in the presence of sodium perboratetetrahydrate or any other alkali metal perborate tetrahydrate adN,N,N',N'-tetraacetyl ethylenediamine (TEAD) according to the bleachstability test as defied in said U.S. Letters Patent No. 4,663,068incorporated by reference herein, the bleach stable deodorant schiffbase having a Malodor Reduction Value of from 0.25 up to 3.0 as measuredby the Malodor Reduction Value test defined in said U.S. Letters PatentNo. 4,663,068 incorporated by reference herein.

The peroxy bleach activator may be exemplified by the following peroxybleach activators:

N,N,N',N'-tetraacetyl ethylenediamine;

N,N,N',N'-tetraacetyl glycoluril;

Glucose pentaacetate;

Sodium acetoxybenzene sulphonate;

Sodium nonanoyloxybenzene sulphonate;

Sodium octanoyloxybenzene sulphonate; and

mixtures thereof.

The non-soap anionic detergent active compound may be selected from thegroup consisting of sodium and potassium alkyl sulphates, sodiumpotassium and ammonium alkyl benzene sulphonates, sodium alkyl glycerylether sulphates, sodium coconut oil fatty acids monoglyceride sulphatesand sulphonates, sodium and potassium salts of sulphuric acid esters ofhigher (C₉ -C₁₈) fatty alcohol-alkylene oxide, the reaction products offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide, sodium and potassium salts of fatty acid amides of methyltaurine, alkane monosulphonates, olefin sulphonates and mixturesthereof.

The nonionic detergent active compound may be selected from the groupconsisting of reaction products of alkylene oxides with alkyl (C₆ -C₂₂)phenols, the condensation products of aliphatic (C₈ -C₁₈) primary orsecondary linear or branched alcohols with ethylene oxide, producs madeby condensation of ethylene oxide with the reaction products ofpropylene oxide and ethylene diamine, long-chain tertiary amine oxides,lone-chain phosphine oxides and dialkyl sulphoxides and mixturesthereof.

What is claimed is:
 1. A compound having the structure: ##STR429##
 2. A compound having the structure: ##STR430##
 3. The compound having the structure: ##STR431##
 4. The compound having the structure: ##STR432##
 5. A process for producing a compound having the structure: ##STR433## comprising the step of effecting the rearrangement of the compound having the structure: ##STR434## according to the over-all reaction: ##STR435## according to the mechanism: ##STR436## comprising the step of heating the compound having the structure: ##STR437## in the absence of acid at a temperature in the range of from about 130° C. up to about 250° C. for a period of time sufficient to form the product having the structure: ##STR438##
 6. The process of claim 5 wherein the compound having the structure: ##STR439## is treated with a base selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate and disodium acid phosphate in the absence of solvent. 